Blends of polyesters containing cyclobutanediol with fluoroalkyl additives and devices made thererom

ABSTRACT

This invention relates to polymer compositions comprising:
         (I) at least one polyester which comprises:
           (a) a dicarboxylic acid component comprising:
               i) 70 to 100 mole % of terephthalic acid residues;   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and   
               (b) a glycol component comprising 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues,   wherein the total mole % of the dicarboxylic acid component is 100 mole %, the total mole % of the glycol component is 100 mole %; and   wherein the inherent viscosity of the polyester is from 0.1 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.; and   
           (II) at least one fluoroalkyl derivative.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 61/938,071 filed Feb. 10, 2014 and U.S. Provisional PatentApplication No. 61/938,066 filed Feb. 10, 2014, the entireties of whichare incorporated herein by reference to the extent not inconsistent withthe present disclosure.

FIELD OF THE INVENTION

The present invention generally relates to compositions comprisingpolyesters containing cyclobutanediol and fluoroalkyl derivatives, anddevices and/or articles made therefrom, for example, medical devices.

BACKGROUND OF THE INVENTION

Polymers such as certain copolyesters, polycarbonates (PC) cellulosics,impact modified acrylic and styrenic, transparent acrylonitrilebutadiene styrene (TABS) are widely used in the medical industry,pharmaceutical industry, bioprocessing industry, and the food industry.Each of these polymers has its own advantages and disadvantages.

A combination of any two or more of the following properties can beimportant in certain industries, for example, in the medical field, thehealth care field, the pharmaceutical field, the bioprocessing field,and the food container and food processing field: optical clarity, goodtoughness, good heat resistance, good lubricity (the capacity to reducefriction and/or properties of a lubricant) such as having a lowcoefficient of friction (COF), good anti-protein binding properties,reduced fibrinogen adsorption, good hydrolytic stability, and goodchemical resistance.

Medical devices are widely used in the healthcare industry to diagnose,mitigate, or prevent disease(s) for patients. These devices include butare not limited to components for infusion and intravenous systems,extracorporeal oxygenators, renal dialyzers catheters, and heart assistdevices, all of which require contact with blood. For certain of thesemedical devices, blood compatibility is an important characteristic. Itis well known that a material's surface properties can affect the eventsof blood protein adsorption and platelet adhesion, particularly when thematerial is used in a medical device. When most foreign surfaces areexposed to blood or other bodily fluids, proteins from the blood and/orbodily fluids adsorb onto them almost immediately, depending on thematerial's surface properties.

It also has become increasingly important to use a material in themedical industry, food industry, and in certain other industries thatthe composition(s), article of manufacture and/or medical devicecontains substantially little to no bisphenol A, the latter beingtypically associated with polycarbonates. A material with anti-proteinbinding properties, including but not limited to reduced fibrinogenadsorption, is of particular interest where living matter (human,animal, organisms, enzymes, etc.) or previously living matter may comeinto contact with the material, for example, the medical industry,health care industry, pharmaceutical industry, bioprocessing industry,food industry, as well as other industries. Bioprocessing refers totreating or preparing a material through a biological process and cangenerally refer to production of a commercially useful biologicalmaterial, chemical, food, drink and/or fuel by biological processes suchas microbial fermentation or degradation.

Therefore, there is a need in the art for compositions having acombination of at least two of the described properties that are usefulin the manufacture of articles of manufacture and/or devices useful inthese industries.

SUMMARY OF THE INVENTION

This invention relates to compositions comprising at least one polyestercomprising residues of terephthalic acid and/or esters thereof such asdimethyl terephthalate and residues of2,2,4,4-tetramethyl-1,3-cyclobutanediol, and at least one fluoroalkylderivative, and articles of manufacture or devices made therefrom

In one embodiment, the invention relates to compositions comprising atleast one polyester comprising an acid component which comprisesresidues of terephthalic acid and isophthalic acid and/or esters thereofsuch as dimethyl terephthalate, and at glycol component comprisingresidues of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and at least onefluoroalkyl derivative, and articles of manufacture or devices madetherefrom.

In one embodiment, the invention relates to compositions comprising atleast one polyester comprising terephthalic acid residues, or an esterthereof, or mixtures thereof, 2,2,4,4-tetramethyl-1,3-cyclobutanediolresidues and 1,4-cyclohexanedimethanol residues, and at least onefluoroalkyl derivative, and articles of manufacture or devices madetherefrom.

In one embodiment, the invention relates to compositions comprising atleast one polyester made from terephthalic acid residues, or an esterthereof, or mixtures thereof, ethylene glycol residues and2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and at least onefluoroalkyl derivative, and articles of manufacture or devices madetherefrom.

In one embodiment, the invention relates to compositions comprising atleast one polyester made from terephthalic acid residues, or an esterthereof, or mixtures thereof, 2,2,4,4-tetramethyl-1,3-cyclobutanediolresidues, 1,4-cyclohexanedimethanol residues, and ethylene glycolresidues, and at least one fluoroalkyl derivative, and articles ofmanufacture or devices made therefrom.

In one embodiment, the fluoroalkyl derivatives useful in all ofpolyester compositions of the invention can be added to the base polymerthrough compounding or blending using techniques known in the art priorto the manufacturing of an article. In one embodiment, the fluoroalkylderivatives(s) is blended with the polymer resulting in the finalpolymer composition of the invention being a blend. The fluoroalkylderivative(s) may be added in step by step increments or simultaneously.

In any of the embodiments of the polyester compositions of theinvention, articles of manufacture including but not limited to medicaldevices, for example, intravenous components, made from the polyestercompositions are contemplated as part of this invention.

In each embodiment, at least one fluoroalkyl derivative can be used. Ineach embodiment, at least one fluoroalkyl derivative can be PM-870additive commercially available from 3M, St. Paul, Minn.

In one aspect, the invention relates to a polyester compositioncomprising at least one fluoroalkyl derivative and at least onepolyester which comprises:

(a) a dicarboxylic acid component comprising:

-   -   i) 70 to 100 mole % of terephthalic acid residues;    -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having        up to 20 carbon atoms; and    -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues        having up to 16 carbon atoms; and

(b) a glycol component comprising 1 to 99 mole % of2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; wherein the total mole% of the dicarboxylic acid component is 100 mole %, the total mole % ofthe glycol component is 100 mole %; and

wherein the inherent viscosity of the polyester is from 0.1 to 1.2 dL/gas determined in 60/40 (wt/wt) phenol/tetrachloroethane at aconcentration of 0.5 g/100 ml at 25° C.; and

wherein the polyester has a Tg of from 80 to 200° C.; and

at least one fluoroalkyl derivative.

In one aspect, the invention relates to a polyester compositioncomprising at least one fluoroalkyl derivative and at least onepolyester which comprises:

(a) a dicarboxylic acid component comprising:

-   -   i) 70 to 100 mole % of terephthalic acid residues;    -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having        up to 20 carbon atoms; and    -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues        having up to 16 carbon atoms; and

(b) a glycol component comprising:

-   -   i) 1 to 99 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol        residues; and    -   ii) 1 to 99 mole % of 1,4-cyclohexanedimethanol residues,

wherein the total mole % of the dicarboxylic acid component is 100 mole%, the total mole % of the glycol component is 100 mole %; and

wherein the inherent viscosity of the polyester is from 0.1 to 1.2 dL/gas determined in 60/40 (wt/wt) phenol/tetrachloroethane at aconcentration of 0.5 g/100 ml at 25° C.; and

wherein the polyester has a Tg of from 80 to 200° C.; and

at least one fluoroalkyl derivative.

In one aspect, the relates to a polyester composition comprising atleast one fluoroalkyl derivative and at least one polyester whichcomprises:

(a) a dicarboxylic acid component comprising:

-   -   i) 70 to 100 mole % of terephthalic acid residues;    -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having        up to 20 carbon atoms; and    -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues        having up to 16 carbon atoms; and

(b) a glycol component comprising:

-   -   i) 10 to 99 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol        residues; and    -   ii) 1 to 90 mole % of 1,4-cyclohexanedimethanol residues,

wherein the total mole % of the dicarboxylic acid component is 100 mole%, the total mole % of the glycol component is 100 mole %; and

wherein the inherent viscosity of the polyester is from 0.1 to 1.2 dL/gas determined in 60/40 (wt/wt) phenol/tetrachloroethane at aconcentration of 0.5 g/100 ml at 25° C.; and

wherein the polyester has a Tg of from 80 to 200° C. comprising at leastone fluoroalkyl derivative and at least one polyester composition.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester and at least one fluoroalkylderivative, which polyester comprises:

(a) a dicarboxylic acid component comprising:

-   -   i) 70 to 100 mole % of terephthalic acid residues;    -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having        up to 20 carbon atoms; and    -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues        having up to 16 carbon atoms; and

(b) a glycol component comprising:

-   -   i) 10 to 30 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol        residues; and    -   ii) 70 to 90 mole % of 1,4-cyclohexanedimethanol residues,

wherein the total mole % of the dicarboxylic acid component is 100 mole%, the total mole % of the glycol component is 100 mole %; and

wherein the inherent viscosity of the polyester is from 0.35 to 1.2 dL/gas determined in 60/40 (wt/wt) phenol/tetrachloroethane at aconcentration of 0.5 g/100 ml at 25° C.; and

wherein the polyester has a Tg of from 90 to 130° C.

In one aspect, the invention relates to a polyester compositioncomprising at least one fluoroalkyl derivative and at least onepolyester, which polyester comprises:

(a) a dicarboxylic acid component comprising:

-   -   i) 70 to 100 mole % of terephthalic acid residues;    -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having        up to 20 carbon atoms; and    -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues        having up to 16 carbon atoms; and

(b) a glycol component comprising:

-   -   i) 15 to 30 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol        residues; and    -   ii) 70 to 85 mole % of 1,4-cyclohexanedimethanol residues,

wherein the total mole % of the dicarboxylic acid component is 100 mole%, the total mole % of the glycol component is 100 mole %; and

wherein the inherent viscosity of the polyester is from 0.35 to 0.75dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at aconcentration of 0.5 g/100 ml at 25° C.; and

wherein the polyester has a Tg of from 80 to 130° C.

In one aspect, the invention relates to a polyester compositioncomprising at least one fluoroalkyl derivative and at least onepolyester which comprises:

(a) a dicarboxylic acid component comprising:

-   -   i) 70 to 100 mole % of terephthalic acid residues;    -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having        up to 20 carbon atoms; and    -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues        having up to 16 carbon atoms; and

(b) a glycol component comprising:

-   -   i) 15 to 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol        residues; and    -   ii) 60 to 85 mole % of 1,4-cyclohexanedimethanol residues,

wherein the total mole % of the dicarboxylic acid component is 100 mole%, the total mole % of the glycol component is 100 mole %; and

wherein the inherent viscosity of the polyester is from 0.35 to 1.0 dL/gas determined in 60/40 (wt/wt) phenol/tetrachloroethane at aconcentration of 0.5 g/100 ml at 25° C.

In one aspect, the invention relates to a polyester compositioncomprising at least one fluoroalkyl derivative and at least onepolyester which comprises:

(a) a dicarboxylic acid component comprising:

-   -   i) 70 to 100 mole % of terephthalic acid residues;    -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having        up to 20 carbon atoms; and    -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues        having up to 16 carbon atoms; and

(b) a glycol component comprising:

-   -   i) 30 to 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol        residues; and    -   ii) 60 to 70 mole % of 1,4-cyclohexanedimethanol residues,

wherein the total mole % of the dicarboxylic acid component is 100 mole%, the total mole % of the glycol component is 100 mole %; and

wherein the inherent viscosity of the polyester is from 0.1 to 1.2 dL/gas determined in 60/40 (wt/wt) phenol/tetrachloroethane at aconcentration of 0.5 g/100 ml at 25° C.

The invention relates to a polyester composition comprising at least onefluoroalkyl derivative and at least one polyester which comprises:

(a) a dicarboxylic acid component comprising:

-   -   i) 70 to 100 mole % of terephthalic acid residues;    -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having        up to 20 carbon atoms; and    -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues        having up to 16 carbon atoms; and

(b) a glycol component comprising:

-   -   i) 1 to 99 mole % of ethylene glycol residues; and    -   ii) 1 to 99 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol        residues, and

wherein the total mole % of the dicarboxylic acid component is 100 mole%, the total mole % of the glycol component is 100 mole %; and

wherein the inherent viscosity of the polyester is from 0.1 to 1.2 dL/gas determined in 60/40 (wt/wt) phenol/tetrachloroethane at aconcentration of 0.5 g/100 ml at 25° C.

In one aspect, the polyesters useful in the invention contain less than15 mole % ethylene glycol residues, such as, for example, 0.01 to lessthan 15 mole % ethylene glycol residues.

In one aspect, the polyesters useful in the invention can contain noethylene glycol residues.

In one aspect, the polyesters useful in the invention contain nobranching agent, or alternatively, at least one branching agent is addedeither prior to or during polymerization of the polyester.

In one aspect, the polyesters useful in the invention contain at leastone branching agent without regard to the method or sequence in which itis added.

In one aspect of the invention, the mole % ofcis-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues useful in certainpolyesters useful in the invention is greater than 50 mole % or greaterthan 55 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol residuesor greater than 70 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediolresidues; wherein the total mole percentage ofcis-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues andtrans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues is equal to atotal of 100 mole %.

In one aspect of the invention, the mole % of the isomers of2,2,4,4-tetramethyl-1,3-cyclobutanediol residues useful in certainpolyesters useful in the invention is from 30 to 70 mole % ofcis-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues or from 30 to 70mole % of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, orfrom 40 to 60 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediolresidues or from 40 to 60 mole % oftrans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, wherein thetotal mole percentage of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediolresidues and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues isequal to a total of 100 mole %.

In one embodiment, the article of manufacture of the invention can beany device known in the art in which one or more of the physicalcharacteristics are useful including but not limited to medical devices,containers, bottles, trays, film or sheet, etc.

Specific potential articles of manufacture and/or packaging can include,for example, medical packaging and/or articles, pharmaceutical packagingand/or articles, other health care packaging and/or articles, packagingand/or articles for bioprocessing, food packaging and/or articles, ordevices made therefrom, for example, medical devices such asthermoformed trays, sterile or non-sterile packaging, steamsterilization bags or pouches, blood bags, tubing, catheters, glucosesensor strips.

The medical devices can include but are not limited to components forinfusion and intravenous systems, extracorporeal oxygenators, renaldialyzers catheters, and heart assist devices

In one embodiment, the medical device can be an intravenous device orcomponent. In one embodiment, the intravenous device or component can bea stopcock. In one embodiment, a stopcock can be an externally operatedvalve regulating the flow of a liquid or gas through a pipe or tube. Inone embodiment, a stopcock can regulate the flow of intravenous fluidsinto a human being.

In one embodiment, two-port, three-port and four-port stopcocks arecontemplated.

In one embodiment, the compositions of the invention and/or the articlesor devices made therefrom, have a combination of any two or more of thefollowing properties: good optical clarity, good toughness, good heatresistance, good lubricity (the capacity to reduce friction and/orproperties of a lubricant) such as having a low coefficient of friction(COF), good anti-protein binding properties, reduced fibrinogenadsorption, hydrolytic stability, and good chemical resistance.

In one embodiment, the compositions of the invention and/or the articlesor devices made therefrom, have a combination of any two or more of thefollowing properties: good optical clarity, good anti-protein bindingproperties such as reduced fibrinogen adsorption, and good lubricity(the capacity to reduce friction and/or properties of a lubricant) suchas having a low coefficient of friction (COF).

In one embodiment, the compositions of the invention and/or the articlesor devices made therefrom, have a combination of any two or more of thefollowing properties: good optical clarity, improved chemicalresistance, and good lubricity, for example, a low coefficient offriction.

In one embodiment, the compositions of the invention and/or the articlesor devices made therefrom, have a combination of good anti-proteinbinding properties such as reduced fibrinogen adsorption and goodlubricity, for example, a low coefficient of friction.

In one embodiment, the compositions of the invention and/or the articlesor devices made therefrom, have a combination of good optical clarityand good anti-protein binding properties such as reduced fibrinogenadsorption.

In one embodiment, the compositions of the invention and/or the articlesor devices made therefrom are optically clear and have good chemicalresistance.

In another embodiment, the fluoroalkyl derivative(s) serves to lower thecoefficient of friction for the polyester, in some cases, substantiallylower.

In another embodiment, the compositions of the invention and/or thearticles or devices made therefrom can have anti-protein bindingproperties. Anti-protein binding properties are defined herein asstopping, preventing, or reducing the frequency and/or extent of proteinbinding.

In one embodiment, the compositions of the invention and/or the articlesor devices made therefrom can have good lubricity.

In one embodiment, the compositions of the invention and/or the articlesor devices made therefrom can have a low coefficient of friction andgood anti-protein binding properties such as reduced fibrinogenadsorption.

In one embodiment, the compositions of the invention and/or the articlesor devices made therefrom can have at least two of the followingproperties: optical clarity, chemically resistant, good anti-proteinbinding properties such as reduced fibrinogen adsorption, and a lowcoefficient of friction.

In one embodiment, the polyester compositions according to the inventioncan adsorb at least 5% less fibrinogen compared to the polyester alone(i.e., without the fluoroalkyl additive) according to the fibrinogenELISA protocol described herein.

In one embodiment, the polyester compositions according to the inventioncan adsorb from 5% to 50% less fibrinogen compared to the polyesteralone (i.e., without the fluoroalkyl additive) according to thefibrinogen ELISA protocol described herein.

In one embodiment, the polyester compositions according to the inventioncan adsorb from 5% to 45% less fibrinogen compared to the polyesteralone (i.e., without the fluoroalkyl additive) according to thefibrinogen ELISA protocol described herein.

In one embodiment, the polyester compositions according to the inventioncan adsorb from 5% to 40% less fibrinogen compared to the polyesteralone (i.e., without the fluoroalkyl additive) according to thefibrinogen ELISA protocol described herein.

In one embodiment, the polyester compositions according to the inventioncan adsorb from 10% to 40% less fibrinogen compared to the polyesteralone (i.e., without the fluoroalkyl additive) according to thefibrinogen ELISA protocol described herein.

In one embodiment, the polyester compositions according to the inventioncan adsorb from 15% to 45% less fibrinogen compared to the polyesteralone (i.e., without the fluoroalkyl additive) according to thefibrinogen ELISA protocol described herein.

The definition of coefficient of friction (COF) is well known in the artand is as follows:

$\mu = \frac{f_{x}}{F_{z}}$

In certain embodiments, the compositions according to the invention havea coefficient of friction (COF) of less than 0.50 as measured with aBruker™ tribometer using a 1″×1″×0.125″ plaque on a 4″×4″×0.125″ plaqueunder a 3 N normal load at 1.2 mm/second.

In certain embodiments, the compositions according to the invention havea coefficient of friction (COF) of 0.10 to 0.50 as measured with aBruker™ tribometer using a 1″×1″×0.125″ plaque on a 4″×4″×0.125″ plaqueunder a 3 N normal load at 1.2 mm/second.

In certain embodiments, the compositions according to the invention havea coefficient of friction (COF) of 0.15 to 0.50 as measured with aBruker™ tribometer using a 1″×1″×0.125″ plaque on a 4″×4″×0.125″ plaqueunder a 3 N normal load at 1.2 mm/second.

In certain embodiments, the compositions according to the invention havea coefficient of friction (COF) of 0.15 to 0.40 as measured with aBruker™ tribometer using a 1″×1″×0.125″ plaque on a 4″×4″×0.125″ plaqueunder a 3 N normal load at 1.2 mm/second.

In certain embodiments, the compositions according to the invention havea coefficient of friction (COF) of 0.15 to 0.35 as measured with aBruker™ tribometer using a 1″×1″×0.125″ plaque on a 4″×4″×0.125″ plaqueunder a 3 N normal load at 1.2 mm/second.

In one embodiment, the polyester compositions according to the inventioncan adsorb at least 5% less fibrinogen compared to the polyester alone(i.e., without the fluoroalkyl additive) according to the fibrinogenELISA protocol described herein and a coefficient of friction (COF) ofless than 0.50 as measured with a Bruker™ tribometer using a1″×1″×0.125″ plaque on a 4″×4″×0.125″ plaque under a 3 N normal load at1.2 mm/second.

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE is a photograph of the test fixture used in the examples forfibrinogen ELISA (enzyme-linked immunosorbent assay).

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to compositions comprising at least one polyestercomprising residues of terephthalic acid and/or esters thereof such asdimethyl terephthalate and residues of2,2,4,4-tetramethyl-1,3-cyclobutanediol, and at least one fluoroalkylderivative, and articles of manufacture or devices made therefrom

In one embodiment, the invention relates to compositions comprising atleast one polyester comprising an acid component which comprisesresidues of terephthalic acid and isophthalic acid and/or esters thereofsuch as dimethyl terephthalate, and at glycol component comprisingresidues of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and at least onefluoroalkyl derivative, and articles of manufacture or devices madetherefrom.

In one embodiment, the invention relates to compositions comprising atleast one polyester comprising terephthalic acid residues, or an esterthereof, or mixtures thereof, 2,2,4,4-tetramethyl-1,3-cyclobutanediolresidues and 1,4-cyclohexanedimethanol residues, and at least onefluoroalkyl derivative, and articles of manufacture or devices madetherefrom.

In one embodiment, the invention relates to compositions comprising atleast one polyester made from terephthalic acid residues, or an esterthereof, or mixtures thereof, ethylene glycol residues and2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and at least onefluoroalkyl derivative, and articles of manufacture or devices madetherefrom.

In one embodiment, the invention relates to compositions comprising atleast one polyester made from terephthalic acid residues, or an esterthereof, or mixtures thereof, 2,2,4,4-tetramethyl-1,3-cyclobutanediolresidues, 1,4-cyclohexanedimethanol residues, and ethylene glycolresidues, and at least one fluoroalkyl derivative, and articles ofmanufacture or devices made therefrom.

The term “polyester”, as used herein, is intended to include“copolyesters” and is understood to mean a synthetic polymer prepared bythe reaction of one or more difunctional carboxylic acids and/ormultifunctional carboxylic acids with one or more difunctional hydroxylcompounds and/or multifunctional hydroxyl compounds. Typically thedifunctional carboxylic acid can be a dicarboxylic acid and thedifunctional hydroxyl compound can be a dihydric alcohol such as, forexample, glycols. Furthermore, as used in this application, the term“diacid” or “dicarboxylic acid” includes multifunctional acids, such asbranching agents. The term “glycol” as used in this applicationincludes, but is not limited to, diols, glycols, and/or multifunctionalhydroxyl compounds. Alternatively, the difunctional carboxylic acid maybe a hydroxy carboxylic acid such as, for example, p-hydroxybenzoicacid, and the difunctional hydroxyl compound may be an aromatic nucleusbearing 2 hydroxyl substituents such as, for example, hydroquinone. Theterm “residue”, as used herein, means any organic structure incorporatedinto a polymer through a polycondensation and/or an esterificationreaction from the corresponding monomer. The term “repeating unit”, asused herein, means an organic structure having a dicarboxylic acidresidue and a diol residue bonded through a carbonyloxy group. Thus, forexample, the dicarboxylic acid residues may be derived from adicarboxylic acid monomer or its associated acid halides, esters, salts,anhydrides, or mixtures thereof. As used herein, therefore, the termdicarboxylic acid is intended to include dicarboxylic acids and anyderivative of a dicarboxylic acid, including its associated acidhalides, esters, half-esters, salts, half-salts, anhydrides, mixedanhydrides, or mixtures thereof, useful in a reaction process with adiol to make polyester. As used herein, the term “terephthalic acid” isintended to include terephthalic acid itself and residues thereof aswell as any derivative of terephthalic acid, including its associatedacid halides, esters, half-esters, salts, half-salts, anhydrides, mixedanhydrides, or mixtures thereof or residues thereof useful in a reactionprocess with a diol to make polyester.

In one embodiment, terephthalic acid may be used as the startingmaterial. In another embodiment, dimethyl terephthalate may be used asthe starting material. In another embodiment, mixtures of terephthalicacid and dimethyl terephthalate may be used as the starting materialand/or as an intermediate material.

The polyesters used in the present invention typically can be preparedfrom dicarboxylic acids and diols which react in substantially equalproportions and are incorporated into the polyester polymer as theircorresponding residues. The polyesters of the present invention,therefore, can contain substantially equal molar proportions of acidresidues (100 mole %) and diol (and/or multifunctional hydroxylcompounds) residues (100 mole %) such that the total moles of repeatingunits is equal to 100 mole %. The mole percentages provided in thepresent disclosure, therefore, may be based on the total moles of acidresidues, the total moles of diol residues, or the total moles ofrepeating units. For example, a polyester containing 30 mole %isophthalic acid, based on the total acid residues, means the polyestercontains 30 mole % isophthalic acid residues out of a total of 100 mole% acid residues. Thus, there are 30 moles of isophthalic acid residuesamong every 100 moles of acid residues. In another example, a polyestercontaining 30 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues,based on the total diol residues, means the polyester contains 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues out of a total of 100mole % diol residues.

Thus, there are 30 moles of 2,2,4,4-tetramethyl-1,3-cyclobutanediolresidues among every 100 moles of diol residues.

In other aspects of the invention, the Tg of the polyesters useful inthe invention can be at least one of the following ranges: 80 to 200°C.; 90 to 200° C.; 90 to 190° C.; 90 to 180° C.; 90 to 170° C.; 90 to160° C.; 90 to 155° C.; 90 to 150° C.; 90 to 145° C.; 90 to 140° C.; 90to 138° C.; 90 to 135° C.; 90 to 130° C.; 90 to 125° C.; 90 to 120° C.;90 to 115° C.; 90 to 110° C.; 90 to 105° C.; 90 to 100° C.; 90 to 95°C.; 95 to 200° C.; 95 to 190° C.; 95 to 180° C.; 95 to 170° C.; 95 to160° C.; 95 to 155° C.; 95 to 150° C.; 95 to 145° C.; 95 to 140° C.; 95to 138° C.; 95 to 135° C.; 95 to 130° C.; 95 to 125° C.; 95 to 120° C.;95 to 115° C.; 95 to 110° C.; 95 to 105° C.; 95 to less than 105° C.; 95to 100° C.; 100 to 200° C.; 100 to 190° C.; 100 to 180° C.; 100 to 170°C.; 100 to 160° C.; 100 to 155° C.; 100 to 150° C.; 100 to 145° C.; 100to 140° C.; 100 to 138° C.; 100 to 135° C.; 100 to 130° C.; 100 to 125°C.; 100 to 120° C.; 100 to 115° C.; 100 to 110° C.; 105 to 200° C.; 105to 190° C.; 105 to 180° C.; 105 to 170° C.; 105 to 160° C.; 105 to 155°C.; 105 to 150° C.; 105 to 145° C.; 105 to 140° C.; 105 to 138° C.; 105to 135° C.; 105 to 130° C.; 105 to 125° C.; 105 to 120° C.; 105 to 115°C.; 105 to 110° C.; greater than 105 to 125° C.; greater than 105 to120° C.; greater than 105 to 115° C.; greater than 105 to 110° C.; 110to 200° C.; 110 to 190° C.; 110 to 180° C.; 110 to 170° C.; 110 to 160°C.; 110 to 155° C.; 110 to 150° C.; 110 to 145° C.; 110 to 140° C.; 110to 138° C.; 110 to 135° C.; 110 to 130° C.; 110 to 125° C.; 110 to 120°C.; 110 to 115° C.; 115 to 200° C.; 115 to 190° C.; 115 to 180° C.; 115to 170° C.; 115 to 160° C.; 115 to 155° C.; 115 to 150° C.; 115 to 145°C.; 115 to 140° C.; 115 to 138° C.; 115 to 135° C.; 110 to 130° C.; 115to 125° C.; 115 to 120° C.; 120 to 200° C.; 120 to 190° C.; 120 to 180°C.; 120 to 170° C.; 120 to 160° C.; 120 to 155° C.; 120 to 150° C.; 120to 145° C.; 120 to 140° C.; 120 to 138° C.; 120 to 135° C.; 120 to 130°C.; 125 to 200° C.; 125 to 190° C.; 125 to 180° C.; 125 to 170° C.; 125to 160° C.; 125 to 155° C.; 125 to 150° C.; 125 to 145° C.; 125 to 140°C.; 125 to 138° C.; 125 to 135° C.; 127 to 200° C.; 127 to 190° C.; 127to 180° C.; 127 to 170° C.; 127 to 160° C.; 127 to 150° C.; 127 to 145°C.; 127 to 140° C.; 127 to 138° C.; 127 to 135° C.; 130 to 200° C.; 130to 190° C.; 130 to 180° C.; 130 to 170° C.; 130 to 160° C.; 130 to 155°C.; 130 to 150° C.; 130 to 145° C.; 130 to 140° C.; 130 to 138° C.; 130to 135° C.; 135 to 200° C.; 135 to 190° C.; 135 to 180° C.; 135 to 170°C.; 135 to 160° C.; 135 to 155° C.; 135 to 150° C.; 135 to 145° C.; 135to 140° C.; 140 to 200° C.; 140 to 190° C.; 140 to 180° C.; 140 to 170°C.; 140 to 160° C.; 140 to 155° C.; 140 to 150° C.; 140 to 145° C.; 148to 200° C.; 148 to 190° C.; 148 to 180° C.; 148 to 170° C.; 148 to 160°C.; 148 to 155° C.; 148 to 150° C.; 150 to 200° C.; 150 to 190° C.; 150to 180° C.; 150 to 170° C.; 150 to 160° C.; 155 to 190° C.; 155 to 180°C.; 155 to 170° C.; and 155 to 165° C.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 99.99 mole %residues of at least one modifying glycol; 1 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 99 mole %residues of at least one modifying glycol; 5 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 95 mole % atleast one modifying glycol; 10 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 90 mole %residues of at least one modifying glycol; 15 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 85 mole %residues of at least one modifying glycol; 20 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 80 mole ° A)residues of at least one modifying glycol; 25 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 75 mole %residues of at least one modifying glycol; 30 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 70 mole %residues of at least one modifying glycol; 35 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 65 mole %residues of at least one modifying glycol; 40 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 60 mole ° A)residues of at least one modifying glycol; 45 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 55 mole %residues of at least one modifying glycol; 50 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 50 mole %residues of at least one modifying glycol; 55 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 45 mole %residues of at least one modifying glycol; 60 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 40 mole %residues of at least one modifying glycol; 65 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 35 mole %residues of at least one modifying glycol; 70 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 30 mole %residues of at least one modifying glycol; 75 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 25 mole %residues of at least one modifying glycol; 80 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 20 mole %residues of at least one modifying glycol; 85 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 15 mole %residues of at least one modifying glycol; 90 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 10 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 99.99 mole %residues of at least one modifying glycol; 1 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 99 mole %residues of at least one modifying glycol; 5 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 95 mole %residues of at least one modifying glycol; 10 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 90 mole %residues of at least one modifying glycol; 15 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 85 mole %residues of at least one modifying glycol; 20 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 80 mole %residues of at least one modifying glycol; 25 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 75 mole %residues of at least one modifying glycol; 30 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 70 mole %residues of at least one modifying glycol; 35 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 65 mole %residues of at least one modifying glycol; 40 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 60 mole %residues of at least one modifying glycol; 45 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 6 to 55 mole %residues of at least one modifying glycol; 50 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 50 mole %residues of at least one modifying glycol; 55 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 45 mole %residues of at least one modifying glycol; 60 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 40 mole %residues of at least one modifying glycol; 65 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 35 mole %residues of at least one modifying glycol; 70 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 30 mole %residues of at least one modifying glycol; 75 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 25 mole %residues of at least one modifying glycol; 80 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 20 mole %residues of at least one modifying glycol; 85 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 15 mole %residues of at least one modifying glycol; 90 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 10 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 99.99 mole %residues of at least one modifying glycol; 1 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 99 mole %residues of at least one modifying glycol; 5 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 95 mole %residues of at least one modifying glycol; 10 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 90 mole %residues of at least one modifying glycol; 15 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 85 mole %residues of at least one modifying glycol; 20 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 80 mole %residues of at least one modifying glycol, 25 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 75 mole %residues of at least one modifying glycol; 30 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 70 mole %residues of at least one modifying glycol; 35 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 65 mole %residues of at least one modifying glycol; 40 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 60 mole %residues of at least one modifying glycol; 45 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 55 mole %residues of at least one modifying glycol; 50 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 50 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 55 to 90 mole %1,4-cyclohexanedimetha 60 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 40 mole %residues of at least one modifying glycol; 65 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 35 mole %residues of at least one modifying glycol; 70 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 30 mole %residues of at least one modifying glycol; 75 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 25 mole %residues of at least one modifying glycol; 80 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 20 mole %residues of at least one modifying glycol; 85 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 15 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 99.99 mole %residues of at least one modifying glycol; 1 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 99 mole %residues of at least one modifying glycol; 5 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 95 mole %residues of at least one modifying glycol; 10 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 90 mole %residues of at least one modifying glycol; 15 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 85 mole %residues of at least one modifying glycol; 20 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 80 mole %residues of at least one modifying glycol; 25 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 75 mole %residues of at least one modifying glycol; 30 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 70 mole %residues of at least one modifying glycol; 35 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 65 mole %residues of at least one modifying glycol; 40 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 60 mole %residues of at least one modifying glycol; 45 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues 15 to 55 mole %residues of at least one modifying glycol; 50 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 50 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 55 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 45 mole %residues of at least one modifying glycol; 60 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 40 mole %residues of at least one modifying glycol; 65 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 35 mole %residues of at least one modifying glycol; 70 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 30 mole %residues of at least one modifying glycol; 75 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 25 mole %residues of at least one modifying glycol; 80 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 20 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 99.99 mole %residues of at least one modifying glycol; 1 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 99 mole %residues of at least one modifying glycol; 5 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 95 mole %residues of at least one modifying glycol; 10 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 90 mole %residues of at least one modifying glycol; 15 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 85 mole %residues of at least one modifying glycol; 20 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 80 mole %residues of at least one modifying glycol; 25 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 75 mole %residues of at least one modifying glycol; 30 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 70 mole %residues of at least one modifying glycol; 35 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 65 mole %residues of at least one modifying glycol; 40 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 60 mole %residues of at least one modifying glycol; 45 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 55 mole %residues of at least one modifying glycol; 50 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 50 mole %residues of at least one modifying glycol; 55 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 45 mole %residues of at least one modifying glycol; 60 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 40 mole %residues of at least one modifying glycol; 65 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 35 mole %residues of at least one modifying glycol; 70 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 30 mole %residues of at least one modifying glycol; and 75 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 25 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 99.99 mole %residues of at least one modifying glycol; 1 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 99 mole %residues of at least one modifying glycol; 5 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 95 mole %residues of at least one modifying glycol; 10 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 90 mole %residues of at least one modifying glycol; 15 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 85 mole %residues of at least one modifying glycol; 20 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 80 mole %residues of at least one modifying glycol; 25 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 75 mole %residues of at least one modifying glycol; 30 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 70 mole %residues of at least one modifying glycol; 35 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 65 mole %residues of at least one modifying glycol; 40 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 60 mole %residues of at least one modifying glycol; 45 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 55 mole %residues of at least one modifying glycol; 50 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 50 mole %residues of at least one modifying glycol; 55 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 45 mole %residues of at least one modifying glycol; 60 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 40 mole %residues of at least one modifying glycol; 65 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 35 mole %residues of at least one modifying glycol; and 70 to 75 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 30 moleresidues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 99.99 mole %residues of at least one modifying glycol; 1 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 99 mole %residues of at least one modifying glycol; 5 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 95 mole %residues of at least one modifying glycol; 10 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 90 mole %residues of at least one modifying glycol; 15 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 85 mole %residues of at least one modifying glycol; 20 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 80 mole %residues of at least one modifying glycol, 25 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 75 mole %residues of at least one modifying glycol; 30 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 70 mole %residues of at least one modifying glycol; 35 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 65 mole %residues of at least one modifying glycol; 40 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 60 mole %residues of at least one modifying glycol; 45 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 55 mole %residues of at least one modifying glycol; 50 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 50 mole %residues of at least one modifying glycol; 55 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 45 mole %residues of at least one modifying glycol; and 60 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 40 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 99.99 mole %residues of at least one modifying glycol; 1 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 99 mole %residues of at least one modifying glycol; 5 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 95 mole %residues of at least one modifying glycol; 10 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 90 mole %residues of at least one modifying glycol; 15 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 85 mole %residues of at least one modifying glycol; 20 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 80 mole %residues of at least one modifying glycol; 25 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 75 mole %residues of at least one modifying glycol; 30 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 70 mole %residues of at least one modifying glycol; 35 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 65 mole %residues of at least one modifying glycol; 40 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 60 mole %residues of at least one modifying glycol; 45 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 55 mole %residues of at least one modifying glycol; 50 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 50 mole %residues of at least one modifying glycol; 55 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 45 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 99.99 mole %residues of at least one modifying glycol; 1 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 99 mole %residues of at least one modifying glycol; 5 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 95 mole %residues of at least one modifying glycol; 10 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 90 mole %residues of at least one modifying glycol; 15 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 85 mole %residues of at least one modifying glycol; 20 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 80 mole %residues of at least one modifying glycol; 25 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 75 mole %residues of at least one modifying glycol; 30 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 70 mole %residues of at least one modifying glycol; 35 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 65 mole %residues of at least one modifying glycol; 40 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 60 mole %residues of at least one modifying glycol; 45 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 55 mole %residues of at least one modifying glycol; and 50 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 50 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 99.99 mole %residues of at least one modifying glycol; 1 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 99 mole %residues of at least one modifying glycol; 5 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 95 mole %residues of at least one modifying glycol; 10 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 90 mole %residues of at least one modifying glycol; 15 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 85 mole %residues of at least one modifying glycol; 20 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 80 mole %residues of at least one modifying glycol 25 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 75 mole %residues of at least one modifying glycol; 30 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 70 mole %residues of at least one modifying glycol; 35 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 65 mole %residues of at least one modifying glycol; 40 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 60 mole %residues of at least one modifying glycol; and 45 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 55 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 99.99 mole %residues of at least one modifying glycol; 1 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 99 mole %residues of at least one modifying glycol; 5 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 95 mole %residues of at least one modifying glycol; 10 to 45 and 55 to 95 mole %residues of at least one modifying glycol mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; 15 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 85 mole %residues of at least one modifying glycol; 20 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 80 mole %residues of at least one modifying glycol; 25 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 75 mole %residues of at least one modifying glycol; 30 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 65 mole %residues of at least one modifying glycol; 35 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 65 mole %residues of at least one modifying glycol; 40 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 60 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 99.99 mole %residues of at least one modifying glycol; 1 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 99 mole %residues of at least one modifying glycol; 5 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 95 mole %residues of at least one modifying glycol; 10 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 90 mole %residues of at least one modifying glycol; 15 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 85 mole %residues of at least one modifying glycol; 20 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 80 mole %residues of at least one modifying glycol; 25 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 75 mole %residues of at least one modifying glycol; 30 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 70 mole %residues of at least one modifying glycol; 35 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 65 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 to 99.99 mole %residues of at least one modifying glycol; 1 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 to 99 mole %residues of at least one modifying glycol; 5 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 to 95 mole %residues of at least one modifying glycol; 10 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 to 90 mole %residues of at least one modifying glycol; 15 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 to 85 mole %residues of at least one modifying glycol; 20 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 to 80 mole %residues of at least one modifying glycol; 25 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 to 75 mole %residues of at least one modifying glycol; 30 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 to 70 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 to 99.99 mole %mole % residues of at least one modifying glycol; 1 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 to 99 mole %residues of at least one modifying glycol; 5 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 to 95 mole %residues of at least one modifying glycol; 10 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 to 90 mole %residues of at least one modifying glycol; 15 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 to 85 mole %residues of at least one modifying glycol; 20 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 to 80 mole %residues of at least one modifying glycol; 25 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 to 75 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75 to 99.99 mole %residues of at least one modifying glycol; 1 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75 to 99 mole %residues of at least one modifying glycol; 5 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75 to 95 mole %residues of at least one modifying glycol; 10 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75 to 90 mole %residues of at least one modifying glycol; 15 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75 to 85 mole %residues of at least one modifying glycol; 20 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75 to 80 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 80 to 99.99 mole %residues of at least one modifying glycol; 1 to 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 80 to 99 mole %residues of at least one modifying glycol; 5 to 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 80 to 95 mole %residues of at least one modifying glycol; 10 to 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 80 to 90 mole %residues of at least one modifying glycol; and 15 to 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 80 to 85 mole %residues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 15 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 85 to 99.99 mole %residues of at least one modifying glycol; 1 to 15 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 85 to 99 mole %residues of at least one modifying glycol; 5 to 15 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 85 to 95 mole %residues of at least one modifying glycol; and 10 to 15 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 85 to 90 moleresidues of at least one modifying glycol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following ranges: 0.01 to 10 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 90 to 99.99 mole %residues of at least one modifying glycol; 1 to 10 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 90 to 99 mole %residues of at least one modifying glycol; 5 to 10 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 90 to 95 mole %residues of at least one modifying glycol; 0.01 to 5 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 95 to 99.99 mole %residues of at least one modifying glycol and 1 to 5 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 95 to 99 mole %residues of at least one modifying glycol.

The glycol component for the polyesters useful in the invention caninclude but is not limited to at least one of the following combinationsof ranges: 10 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediolresidues and 1 to 90 mole % 1,4-cyclohexanedimethanol residues; 10 to 95mole 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 90 mole %1,4-cyclohexanedimethanol residues; 10 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 90 mole %1,4-cyclohexanedimethanol residues; 10 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 90 mole %1,4-cyclohexanedimethanol residues; 10 to 80 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 90 mole %1,4-cyclohexanedimethanol residues, 10 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 90 mole %1,4-cyclohexanedimethanol residues; 10 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 30 to 90 mole %1,4-cyclohexanedimethanol residues; 10 to 65 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 90 mole %1,4-cyclohexanedimethanol residues; 10 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 90 mole %1,4-cyclohexanedimethanol residues; 10 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 90 mole %1,4-cyclohexanedimethanol residues; 10 to 50 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 90 mole %1,4-cyclohexanedimethanol residues; 10 to less than 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and greater than 50 to90 mole 1,4-cyclohexanedimethanol residues; 10 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 90 mole %1,4-cyclohexanedimethanol residues; 10 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 90 mole %1,4-cyclohexanedimethanol residues; 10 to 35 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 to 90 mole %1,4-cyclohexanedimethanol residues; 10 to less than 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and greater than 65 upto 90 mole 1,4-cyclohexanedimethanol residues; 10 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 to 90 mole %1,4-cyclohexanedimethanol residues; 10 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and greater than 75 to90 mole % 1,4-cyclohexanedimethanol residues; 11 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75 to 89 mole %1,4-cyclohexanedimethanol residues; 12 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75 to 88 mole %1,4-cyclohexanedimethanol residues; and 13 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75 to 87 mole %1,4-cyclohexanedimethanol residues;

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 15 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 85 mole %1,4-cyclohexanedimethanol residues; 15 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 85 mole %1,4-cyclohexanedimethanol residues; 15 to 90 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 85 mole %1,4-cyclohexanedimethanol residues; 15 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 85 mole %1,4-cyclohexanedimethanol residues; 15 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 85 mole %1,4-cyclohexanedimethanol residues, 15 to 75 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 85 mole %1,4-cyclohexanedimethanol residues; 15 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 30 to 85 mole %1,4-cyclohexanedimethanol residues; 15 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 85 mole %1,4-cyclohexanedimethanol residues; 15 to 60 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 85 mole %1,4-cyclohexanedimethanol residues; 15 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 85 mole %1,4-cyclohexanedimethanol residues; and 15 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 85 mole %1,4-cyclohexanedimethanol residues.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 15 to less than 50mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and greater than50 up to 85 mole 1,4-cyclohexanedimethanol residues; 15 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 85 mole %1,4-cyclohexanedimethanol residues; 15 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 85 mole %1,4-cyclohexanedimethanol residues; 15 to 35 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 to 85 mole %1,4-cyclohexanedimethanol residues; 15 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 to 85 mole %1,4-cyclohexanedimethanol residues; 15 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75 to 85 mole %1,4-cyclohexanedimethanol residues; 15 to 20 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75 to 80 mole %1,4-cyclohexanedimethanol residues; and 17 to 23 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 77 to 83 mole %1,4-cyclohexanedimethanol residues.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 20 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 80 mole %1,4-cyclohexanedimethanol residues; 20 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 80 mole %1,4-cyclohexanedimethanol residues; 20 to 90 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 80 mole %1,4-cyclohexanedimethanol residues; 20 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 80 mole %1,4-cyclohexanedimethanol residues; 20 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 80 mole %1,4-cyclohexanedimethanol residues, 20 to 75 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 80 mole %1,4-cyclohexanedimethanol residues; 20 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 30 to 80 mole %1,4-cyclohexanedimethanol residues; 20 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 80 mole %1,4-cyclohexanedimethanol residues; 20 to 60 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 80 mole %1,4-cyclohexanedimethanol residues; 20 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 80 mole %1,4-cyclohexanedimethanol residues; 20 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 80 mole %1,4-cyclohexanedimethanol residues; 20 to 45 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 80 mole %1,4-cyclohexanedimethanol residues; 20 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 80 mole %1,4-cyclohexanedimethanol residues; 20 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 to 80 mole %1,4-cyclohexanedimethanol residues; 20 to 30 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 to 80 mole %1,4-cyclohexanedimethanol residues; and 20 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75 to 80 mole %1,4-cyclohexanedimethanol residues.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 25 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 75 mole %1,4-cyclohexanedimethanol residues; 25 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 75 mole %1,4-cyclohexanedimethanol residues; 25 to 90 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 75 mole %1,4-cyclohexanedimethanol residues; 25 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 75 mole %1,4-cyclohexanedimethanol residues; 25 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 75 mole %1,4-cyclohexanedimethanol residues, 25 to 75 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 75 mole %1,4-cyclohexanedimethanol residues; 25 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 30 to 75 mole %1,4-cyclohexanedimethanol residues; 25 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 75 mole %1,4-cyclohexanedimethanol residues; 25 to 60 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 75 mole %1,4-cyclohexanedimethanol residues; 25 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 75 mole %1,4-cyclohexanedimethanol residues; 25 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 75 mole %1,4-cyclohexanedimethanol residues; 25 to 45 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 75 mole %1,4-cyclohexanedimethanol residues; 25 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 75 mole %1,4-cyclohexanedimethanol residues; 25 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 to 75 mole %1,4-cyclohexanedimethanol residues; and 25 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 to 75 mole %1,4-cyclohexanedimethanol residues.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 30 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 70 mole %1,4-cyclohexanedimethanol residues; 30 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 70 mole %1,4-cyclohexanedimethanol residues; 30 to 90 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 70 mole %1,4-cyclohexanedimethanol residues; 30 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 70 mole %1,4-cyclohexanedimethanol residues; 30 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 70 mole %1,4-cyclohexanedimethanol residues, 30 to 75 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 70 mole %1,4-cyclohexanedimethanol residues; 30 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 30 to 70 mole %1,4-cyclohexanedimethanol residues; 30 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 70 mole %1,4-cyclohexanedimethanol residues; 30 to 60 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 70 mole %1,4-cyclohexanedimethanol residues; 30 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 70 mole %1,4-cyclohexanedimethanol residues; 30 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 70 mole %1,4-cyclohexanedimethanol residues; 30 to less than 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and greater than 50 to70 mole % 1,4-cyclohexanedimethanol residues; 30 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 70 mole %1,4-cyclohexanedimethanol residues; 30 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 70 mole %1,4-cyclohexanedimethanol residues; 30 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 to 70 mole %1,4-cyclohexanedimethanol residues.

In other aspects of the invention, the glycol component for thepolyesters useful in the of the invention include but are not limited toat least one of the following combinations of ranges: 35 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 65 mole %1,4-cyclohexanedimethanol residues; 35 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 65 mole %1,4-cyclohexanedimethanol residues; 35 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 65 mole %1,4-cyclohexanedimethanol residues; 35 to 85 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 65 mole %1,4-cyclohexanedimethanol residues; 35 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 65 mole %1,4-cyclohexanedimethanol residues, 35 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 65 mole %1,4-cyclohexanedimethanol residues; 35 to 70 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 30 to 65 mole %1,4-cyclohexanedimethanol residues; 35 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 65 mole %1,4-cyclohexanedimethanol residues; 35 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 65 mole %1,4-cyclohexanedimethanol residues; 35 to 55 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 65 mole %1,4-cyclohexanedimethanol residues; 35 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 65 mole %1,4-cyclohexanedimethanol residues; 35 to less than 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and greater than 50 to65 mole % 1,4-cyclohexanedimethanol residues; 35 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 65 mole %1,4-cyclohexanedimethanol residues; 35 to 40 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 65 mole %1,4-cyclohexanedimethanol residues.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 40 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 60 mole %1,4-cyclohexanedimethanol residues; 40 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 60 mole %1,4-cyclohexanedimethanol residues; 40 to 90 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 60 mole %1,4-cyclohexanedimethanol residues; 40 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 60 mole %1,4-cyclohexanedimethanol residues; 40 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 60 mole %1,4-cyclohexanedimethanol residues, 40 to 75 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 60 mole %1,4-cyclohexanedimethanol residues; 40 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 30 to 60 mole %1,4-cyclohexanedimethanol residues; 40 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 60 mole %1,4-cyclohexanedimethanol residues; 40 to 60 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 60 mole %1,4-cyclohexanedimethanol residues; 40 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 60 mole %1,4-cyclohexanedimethanol residues; 40 to less than 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and greater than 50 to60 mole % 1,4-cyclohexanedimethanol residues; 40 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 60 mole %1,4-cyclohexanedimethanol residues; and 40 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 to 60 mole %1,4-cyclohexanedimethanol residues.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 45 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 1 to 55 mole %1,4-cyclohexanedimethanol residues; 45 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 5 to 55 mole %1,4-cyclohexanedimethanol residues; 45 to 90 mole2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 10 to 55 mole %1,4-cyclohexanedimethanol residues; 45 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 15 to 55 mole %1,4-cyclohexanedimethanol residues; 45 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 20 to 55 mole %1,4-cyclohexanedimethanol residues, 45 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 25 to 55 mole %1,4-cyclohexanedimethanol residues; 45 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 30 to 55 mole %1,4-cyclohexanedimethanol residues; 45 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 35 to 55 mole %1,4-cyclohexanedimethanol residues; 45 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 55 mole %1,4-cyclohexanedimethanol residues; greater than 45 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to less than 55mole % 1,4-cyclohexanedimethanol residues; 45 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 55 mole %1,4-cyclohexanedimethanol residues; and 45 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 55 mole %1,4-cyclohexanedimethanol residues.

For certain embodiments of the invention, the polyesters useful in theinvention may exhibit at least one of the following inherent viscositiesas determined in 60/40 (wt/wt) phenol/tetrachloroethane at aconcentration of 0.5 g/100 ml at 25° C.: 0.45 to 1.2 dL/g; 0.45 to 1.1dL/g; 0.45 to 1 dL/g; 0.45 to 0.98 dL/g; 0.45 to 0.95 dL/g; 0.45 to 0.90dL/g; 0.45 to 0.85 dL/g; 0.45 to 0.80 dL/g; 0.45 to 0.75 dL/g; 0.45 toless than 0.75 dL/g; 0.45 to 0.72 dL/g; 0.45 to 0.70 dL/g; 0.45 to lessthan 0.70 dL/g; 0.45 to 0.68 dL/g; 0.45 to less than 0.68 dL/g; 0.45 to0.65 dL/g; 0.50 to 1.2 dL/g; 0.50 to 1.1 dL/g; 0.50 to 1 dL/g; 0.50 toless than 1 dL/g; 0.50 to 0.98 dL/g; 0.50 to 0.95 dL/g; 0.50 to 0.90dL/g; 0.50 to 0.85 dL/g; 0.50 to 0.80 dL/g; 0.50 to 0.75 dL/g; 0.50 toless than 0.75 dL/g; 0.50 to 0.72 dL/g; 0.50 to 0.70 dL/g; 0.50 to lessthan 0.70 dL/g; 0.50 to 0.68 dL/g; 0.50 to less than 0.68 dL/g; 0.50 to0.65 dL/g; 0.55 to 1.2 dL/g; 0.55 to 1.1 dL/g; 0.55 to 1 dL/g; 0.55 toless than 1 dL/g; 0.55 to 0.98 dL/g; 0.55 to 0.95 dL/g; 0.55 to 0.90dL/g; 0.55 to 0.85 dL/g; 0.55 to 0.80 dL/g; 0.55 to 0.75 dL/g; 0.55 toless than 0.75 dL/g; 0.55 to 0.72 dL/g; 0.55 to 0.70 dL/g; 0.55 to lessthan 0.70 dL/g; 0.55 to 0.68 dL/g; 0.55 to less than 0.68 dL/g; 0.55 to0.65 dL/g; 0.58 to 1.2 dL/g; 0.58 to 1.1 dL/g; 0.58 to 1 dL/g; 0.58 toless than 1 dL/g; 0.58 to 0.98 dL/g; 0.58 to 0.95 dL/g; 0.58 to 0.90dL/g; 0.58 to 0.85 dL/g; 0.58 to 0.80 dL/g; 0.58 to 0.75 dL/g; 0.58 toless than 0.75 dL/g; 0.58 to 0.72 dL/g; 0.58 to 0.70 dL/g; 0.58 to lessthan 0.70 dL/g; 0.58 to 0.68 dL/g; 0.58 to less than 0.68 dL/g; 0.58 to0.65 dL/g; 0.60 to 1.2 dL/g; 0.60 to 1.1 dL/g; 0.60 to 1 dL/g; 0.60 toless than 1 dL/g; 0.60 to 0.98 dL/g; 0.60 to 0.95 dL/g; 0.60 to 0.90dL/g; 0.60 to 0.85 dL/g; 0.60 to 0.80 dL/g; 0.60 to 0.75 dL/g; 0.60 toless than 0.75 dL/g; 0.60 to 0.72 dL/g; 0.60 to 0.70 dL/g; 0.60 to lessthan 0.70 dL/g; 0.60 to 0.68 dL/g; 0.60 to less than 0.68 dL/g; 0.60 to0.65 dL/g; 0.65 to 1.2 dL/g; 0.65 to 1.1 dL/g; 0.65 to 1 dL/g; 0.65 toless than 1 dL/g; 0.65 to 0.98 dL/g; 0.65 to 0.95 dL/g; 0.65 to 0.90dL/g; 0.65 to 0.85 dL/g; 0.65 to 0.80 dL/g; 0.65 to 0.75 dL/g; 0.65 toless than 0.75 dL/g; 0.65 to 0.72 dL/g; 0.65 to 0.70 dL/g; 0.65 to lessthan 0.70 dL/g; 0.68 to 1.2 dL/g; 0.68 to 1.1 dL/g; 0.68 to 1 dL/g; 0.68to less than 1 dL/g; 0.68 to 0.98 dL/g; 0.68 to 0.95 dL/g; 0.68 to 0.90dL/g; 0.68 to 0.85 dL/g; 0.68 to 0.80 dL/g; 0.68 to 0.75 dL/g; 0.68 toless than 0.75 dL/g; 0.68 to 0.72 dL/g; greater than 0.76 dL/g to 1.2dL/g

It is contemplated that polyesters useful in the invention can possessat least one of the inherent viscosity ranges described herein and atleast one of the monomer ranges for the compositions described hereinunless otherwise stated. It is also contemplated that polyesters usefulin the the invention can possess at least one of the Tg ranges describedherein and at least one of the monomer ranges for the compositionsdescribed herein unless otherwise stated. Further, it is contemplatedthat polyesters useful in the invention can possess at least one of theTg ranges described herein, at least one of the inherent viscosityranges described herein, and at least one of the monomer ranges for thecompositions described herein unless otherwise stated.

For the desired polyester, the molar ratio of cis/trans2,2,4,4-tetramethyl-1,3-cyclobutanediol residues can vary from the pureform of each or mixtures thereof. In certain embodiments, the molarpercentages for cis and/or trans2,2,4,4,-tetramethyl-1,3-cyclobutanediol residues are greater than 50mole % cis and less than 50 mole % trans; or greater than 55 mole % cisand less than 45 mole % trans; or 30 to 70 mole % cis and 70 to 30%trans; or 40 to 60 mole % cis and 60 to 40 mole % trans; or 50 to 70mole % trans and 50 to 30% cis or 50 to 70 mole % cis and 50 to 30%trans; or 60 to 70 mole % cis and 30 to 40 mole % trans; or greater than70 mole cis and less than 30 mole % trans; wherein the total sum of themole percentages for cis- andtrans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues is equal to 100mole %. The molar ratio of cis/trans 1,4-cyclohexanedimethanol can varywithin the range of 50/50 to 0/100, such as between 40/60 to 20/80.

In certain embodiments, terephthalic acid or an ester thereof, such as,for example, dimethyl terephthalate, or a mixture of terephthalic acidand an ester thereof, makes up most or all of the dicarboxylic acidcomponent used to form the polyesters useful in the invention. Incertain embodiments, terephthalic acid residues can make up a portion orall of the dicarboxylic acid component used to form the presentpolyester at a concentration of at least 70 mole %, such as at least 80mole %, at least 90 mole %, at least 95 mole %, at least 99 mole %, or100 mole %. In certain embodiments, higher amounts of terephthalic acidcan be used in order to produce a higher impact strength polyester. Inone embodiment, dimethyl terephthalate is part or all of thedicarboxylic acid component used to make the polyesters useful in thepresent invention. For the purposes of this disclosure, the terms“terephthalic acid” and “dimethyl terephthalate” are usedinterchangeably herein. In all embodiments, any amount of terephthalicacid may be used, for example, ranges of from 50 to 100 mole %, 55 to100 mole %, 60 to 100 mole %, 65 to 100 mole %, 70 to 100 mole %; or 80to 100 mole %; or 90 to 100 mole %; or 99 to 100 mole %; or 100 mole %terephthalic acid and/or dimethyl terephthalate and/or mixtures thereofmay be used.

In addition to terephthalic acid, the dicarboxylic acid component of thepolyester useful in the invention can comprise up to 50 mole %, up to 45mole %, up to 40 mole %, up to 35 mole %, up to 30 mole %, up to 25 mole%, up to 20 mole %, up to 15 mole %, up to 10 mole %, up to 5 mole %, orup to 1 mole % of one or more modifying aromatic dicarboxylic acids. Yetanother embodiment contains 0 mole % modifying aromatic dicarboxylicacids. Thus, if present, it is contemplated that the amount of one ormore modifying aromatic dicarboxylic acids can range from any of thesepreceding endpoint values including, for example, from 0.01 to 50 mole%, 0.01 to 45 mole %, 0.01 to 40 mole %, 0.01 to 35 mole %, 0.01 to 30mole %, 0.01 to 25 mole %, 0.01 to 20 mole %, 0.01 to 15 mole % from0.01 to 10 mole %, from 0.01 to 5 mole % and from 0.01 to 1 mole. In oneembodiment, modifying aromatic dicarboxylic acids that may be used inthe present invention include but are not limited to those having up to20 carbon atoms, and which can be linear, para-oriented, or symmetrical.Examples of modifying aromatic dicarboxylic acids which may be used inthis invention include, but are not limited to, isophthalic acid,4,4′-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-,2,7-naphthalenedicarboxylic acid, and trans-4,4′-stilbenedicarboxylicacid, and esters thereof. In one embodiment, the modifying aromaticdicarboxylic acid is isophthalic acid.

The carboxylic acid component of the polyesters useful in the inventioncan be further modified with up to 10 mole %, such as up to 5 mole % orup to 1 mole % of one or more aliphatic dicarboxylic acids containing2-16 carbon atoms, such as, for example, malonic, succinic, glutaric,adipic, pimelic, suberic, azelaic and dodecanedioic dicarboxylic acids.Certain embodiments can also comprise 0.01 or more mole %, such as 0.1or more mole %, 1 or more mole %, 5 or more mole %, or 10 or more mole %of one or more modifying aliphatic dicarboxylic acids. Yet anotherembodiment contains 0 mole % modifying aliphatic dicarboxylic acids.Thus, if present, it is contemplated that the amount of one or moremodifying aliphatic dicarboxylic acids can range from any of thesepreceding endpoint values including, for example, from 0.01 to 10 mole %and from 0.1 to 10 mole %. The total mole % of the dicarboxylic acidcomponent is 100 mole %.

Esters of terephthalic acid and the other modifying dicarboxylic acidsor their corresponding esters and/or salts may be used instead of thedicarboxylic acids. Suitable examples of dicarboxylic acid estersinclude, but are not limited to, the dimethyl, diethyl, dipropyl,diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the estersare chosen from at least one of the following: methyl, ethyl, propyl,isopropyl, and phenyl esters.

The 1,4-cyclohexanedimethanol residues may be cis, trans, or a mixturethereof, for example a cis/trans ratio of 60:40 to 40:60. In anotherembodiment, the trans-1,4-cyclohexanedimethanol residues can be presentin an amount of 60 to 80 mole %.

In one embodiment, the glycol component of the polyester portion of thepolyester composition useful in the invention can contain 25 mole % orless of one or more modifying glycols which are not2,2,4,4-tetramethyl-1,3-cyclobutanediol residues or1,4-cyclohexanedimethanol residues; in one embodiment, the polyestersuseful in the invention may contain less than 15 mole % of one or moremodifying glycols. In another embodiment, the polyesters useful in theinvention can contain 10 mole % or less of one or more modifyingglycols. In another embodiment, the polyesters useful in the inventioncan contain 5 mole % or less of one or more modifying glycols. Inanother embodiment, the polyesters useful in the invention can contain 3mole % or less of one or more modifying glycols. In another embodiment,the polyesters useful in the invention can contain 0 mole modifyingglycols. Certain embodiments can also contain 0.01 or more mole %, suchas 0.1 or more mole %, 1 or more mole %, 5 or more mole %, or 10 or moremole % of one or more modifying glycols. Thus, if present, it iscontemplated that the amount of one or more modifying glycols can rangefrom any of these preceding endpoint values including, for example, from0.01 to 15 mole % and from 0.1 to 10 mole %.

Modifying glycols useful in the polyesters useful in the invention referto diols other than 2,2,4,4-tetramethyl-1,3-cyclobutanediol and maycontain 2 to 16 carbon atoms. Examples of suitable modifying glycolsinclude, but are not limited to, ethylene glycol residues,1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, neopentylglycol, ethylene glycol, 1,4-butanediol, 1,5-pentanediol,1,6-hexanediol, p-xylene glycol or mixtures thereof. In one embodiment,the modifying glycol is ethylene glycol. In one embodiment, themodifying glycol is 1,4-cyclohexanedimethanol. In another embodiment,ethylene glycol is excluded as a modifying diol. In another embodiment,the modifying glycols are 1,3-propanediol and/or 1,4-butanediol.

The polyesters useful in the polyesters compositions of the inventioncan comprise from 0 to 10 mole percent, for example, from 0.01 to 5 molepercent, from 0.01 to 1 mole percent, from 0.05 to 5 mole percent, from0.05 to 1 mole percent, or from 0.1 to 0.7 mole percent, based the totalmole percentages of either the diol or diacid residues; respectively, ofone or more residues of a branching monomer, also referred to herein asa branching agent, having 3 or more carboxyl substituents, hydroxylsubstituents, or a combination thereof. In certain embodiments, thebranching monomer or agent may be added prior to and/or during and/orafter the polymerization of the polyester. The polyester(s) useful inthe invention can thus be linear or branched. The polycarbonate can alsobe linear or branched. In certain embodiments, the branching monomer oragent may be added prior to and/or during and/or after thepolymerization of the polycarbonate.

Examples of branching monomers include, but are not limited to,multifunctional acids or multifunctional alcohols such as trimelliticacid, trimellitic anhydride, pyromellitic dianhydride,trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaricacid, 3-hydroxyglutaric acid and the like. In one embodiment, thebranching monomer residues can comprise 0.1 to 0.7 mole percent of oneor more residues chosen from at least one of the following: trimelliticanhydride, pyromellitic dianhydride, glycerol, sorbitol,1,2,6-hexanetriol, pentaerythritol, trimethylolethane, and/or trimesicacid. The branching monomer may be added to the polyester reactionmixture or blended with the polyester in the form of a concentrate asdescribed, for example, in U.S. Pat. Nos. 5,654,347 and 5,696,176, whosedisclosure regarding branching monomers is incorporated herein byreference.

The glass transition temperature (Tg) of the polyesters useful in theinvention was determined using a TA DSC 2920 from Thermal AnalystInstrument at a scan rate of 20° C./min.

In one embodiment, certain polyesters useful in this invention arevisually clear. The term “visually clear” is defined herein as anappreciable absence of cloudiness, haziness, and/or muddiness, wheninspected visually.

In one embodiment, polyesters of this invention exhibit superior notchedtoughness in thick sections. Notched Izod impact strength, as describedin ASTM D256, is a common method of measuring toughness.

The polyesters useful in the invention can possess one or more of thefollowing properties. In one embodiment, the polyesters useful in theinvention exhibit a notched Izod impact strength of at least 150 J/m (3ft-lb/in) at 23° C. with a 10-mil notch in a 3.2 mm (⅛-inch) thick bardetermined according to ASTM D256; in one embodiment, the polyestersuseful in the invention exhibit a notched Izod impact strength of atleast (400 J/m) 7.5 ft-lb/in at 23° C. with a 10-mil notch in a 3.2 mm(⅛-inch) thick bar determined according to ASTM D256; in one embodiment,the polyesters useful in the invention exhibit a notched Izod impactstrength of at least (10 ft-lb/in) at 23° C. with a 10-mil notch in a3.2 mm (⅛-inch) thick bar determined according to ASTM D256 in oneembodiment, the polyesters useful in the invention exhibit a notchedIzod impact strength of at least 1000 J/m (18 ft-lb/in) at 23° C. with a10-mil notch in a 3.2 mm (⅛-inch) thick bar determined according to ASTMD256. In one embodiment, the polyesters useful in the invention exhibita notched Izod impact strength of at least 150 J/m (3 ft-lb/in) at 23°C. with a 10-mil notch in a 6.4 mm (¼-inch) thick bar determinedaccording to ASTM D256; in one embodiment, the polyesters useful in theinvention exhibit a notched Izod impact strength of at least (400 J/m)7.5 ft-lb/in at 23° C. with a 10-mil notch in a 6.4 mm (¼-inch) thickbar determined according to ASTM D256; in one embodiment, the polyestersuseful in the invention exhibit a notched Izod impact strength of atleast 1000 J/m (18 ft-lb/in) at 23° C. with a 10-mil notch in a 6.4 mm(¼-inch) thick bar determined according to ASTM D256.

In one embodiment, the polyesters useful in the invention and/or thepolyester compositions of the invention in combination with thefluoroalkyl derivatives useful in the invention, with or without toners,can have color values L*, a* and b*, which can be determined using aHunter Lab Ultrascan Spectra Colorimeter manufactured by HunterAssociates Lab Inc., Reston, Va. The color determinations are averagesof values measured on either pellets of the polyesters or plaques orother items injection molded or extruded from them. They are determinedby the L*a*b* color system of the CIE (International Commission onIllumination) (translated), wherein L* represents the lightnesscoordinate, a* represents the red/green coordinate, and b* representsthe yellow/blue coordinate. In certain embodiments, the b* values forthe polyesters useful in the invention can be from −10 to less than 10and the L* values can be from 50 to 90. In other embodiments, the b*values for the polyesters useful in the invention can be present in oneof the following ranges: −10 to 9; −10 to 8; −10 to 7; −10 to 6; −10 to5; −10 to 4; −10 to 3; −10 to 2; from −5 to 9; −5 to 8; −5 to 7; −5 to6; −5 to 5; −5 to 4; −5 to 3; −5 to 2; 0 to 9; 0 to 8; 0 to 7; 0 to 6; 0to 5; 0 to 4; 0 to 3; 0 to 2; 1 to 10; 1 tog; 1 to 8; 1 to 7; 1 to 6; 1to 5; 1 to 4; 1 to 3; and 1 to 2. In other embodiments, the L* value forthe polyesters useful in the invention can be present in one of thefollowing ranges: 50 to 60; 50 to 70; 50 to 80; 50 to 90; 60 to 70; 60to 80; 60 to 90; 70 to 80; 79 to 90.

Reduced Fibrinogen Adsorption

Medical devices that come into contact with blood often require plasticswhich are designed or engineered to reduce or minimize thrombosis orblood clotting properties. Other than the blood itself and the flowrate, the device material is one of the most important variablesaffecting blood coagulation. Fibrinogen is the principal protein invertebrates that is involved in the formation of blood clots.

It is well known that a material's surface properties can affect theinitial events of blood protein adsorption and platelet adhesion. Whenmost foreign surfaces are exposed to blood, proteins from the bloodadsorb onto them almost immediately, depending on the materials' surfaceproperties. Due to the complexity of blood compatibility, it isdifficult to correlate surface properties directly with blood responsein order to predict device performance. However, the amount of adsorbedplasma proteins, such as fibrinogen, on a material's surface is verymeaningful for regulating platelet adhesion, migration of cellularcomponents, and subsequent blood clotting. The measurement of proteinadsorption can predict levels of platelet adhesion, and thus providevaluable information to evaluate regional thrombus formation.

To evaluate the blood-clotting properties of plastics, an enzyme-linkedimmunosorbent assay (ELISA) has been developed to detect the presence offibrinogen adsorbed on a sample. Generally, the fibrinogen ELISAprocedure involves attaching the protein to the surface of the sample ina disposable microtiter plate, and then applying an antibody over thesurface to bind to the protein. The degree of antibody binding isdetermined by activity of the enzyme that is conjugated to the antibody.Detection of that activity is typically through the use of a chromogenicsubstrate for the enzyme. The extent of color change is proportional tothe amount of adsorbed protein present and is typically measuredspectrophotometrically using a plate reader.

In one embodiment, the fibrinogen ELISA procedure/protocol includes thefollowing steps: (1) incubating the polymer sample in flexural bar formin a phosphate-buffered saline solution containing 0.5 mg/mL offibrinogen and 2% of bovine serum albumin (w/v) for 5 minutes; (2)removing unbound fibrinogen from the sample bar by washing the bar withphosphate-buffered saline having a pH of 7.3 three times; (3) incubatingthe sample bar in a non-animal protein blocking agent for 30 minutes at37° C.; (4) incubating the bar in a 1 μg/mL solution of ananti-fibrinogen horseradish peroxidase antibody-conjugate in anon-animal protein-blocked microtiter plate for 60 minutes at 37° C.;(5) washing the bar four times with a diluted TBST buffer to removeexcess non-specific binding of the antibody-conjugate; (6) incubatingthe bar with an enzyme substrate 3,3′,5,5′-tetramethylbenzidine for 60minutes; (7) removing the bar from the microplate containing the enzymesubstrate; and (8) measuring the absorbance of the enzyme substrate inthe microplate well using a microplate spectrophotometer at 630nanometers to detect conversion of the enzyme substrate to the blueproduct.

In one embodiment, the fibrinogen ELISA procedure/protocol includes thefollowing steps: (1) incubating the polymer sample in flexural bar formin a phosphate-buffered saline solution containing 0.5 mg/mL offibrinogen and 2% of bovine serum albumin (w/v) for 5 minutes; (2)removing unbound fibrinogen from the sample bar by washing the bar withphosphate-buffered saline (PBS) three times; (3) incubating the samplebar in a non-animal protein blocking agent (NAP-Blocker™) for 30 minutesat 37° C. to block unoccupied binding sites on the bar; (4) incubatingthe bar in a 1 μg/mL solution of an anti-fibrinogen horseradishperoxidase (HRP) antibody-conjugate in a NAP-blocked microtiter platefor 60 minutes at 37° C.; (5) washing the bar in a diluted TBST buffer(mixture of Tris-Buffered Saline and Tween® 20) (pH=7.5) four times toremove excess non-specific binding of the antibody-conjugate; (6)incubating the bar with an enzyme substrate(3,3′,5,5′-tetramethylbenzidine) for 60 minutes; (7) removing the barfrom the microplate containing the enzyme substrate; and (8) measuringthe absorbance of the enzyme substrate in the microplate well using amicroplate spectrophotometer at 630 nm to detect conversion of theenzyme substrate to the blue product.

The PBS is a 0.01 M phosphate-buffered solution containing 0.0027 M ofpotassium chloride and 0.137 M of sodium chloride with a pH of 7.4 at25° C.

As used herein, “TBST buffer” refers to a mixture of 90.11 wt % ofdeionized water, 8.77 wt % of sodium chloride, 1.12 wt % of Tris, and0.002 wt % of Tween® 20 (which is polysorbate 20). “Diluted TBST buffer”refers to TBST buffer that has been diluted 10 times (10×) withdeionized water.

Preferably, the compositions according to the invention adsorb at least5% less fibrinogen than the polyester alone (i.e., without thefluoroalkyl additive) according to the fibrinogen ELISA protocol. Incertain embodiments, the compositions according to the invention adsorbat least 10% less, at least 15% less, at least 20% less, at least 25%less, at least 30% less, at least 35% less, at least 40% less, or atleast 45% less fibrinogen than the polyester alone according to thefibrinogen ELISA protocol. In other embodiments, the compositionsaccording to the invention adsorb 5 to 50% less fibrinogen, 10 to 50%less fibrinogen, 15 to 50% less fibrinogen, 20 to 50% less fibrinogen,25 to 50% less fibrinogen, 30 to 50% less fibrinogen, 35 to 50% lessfibrinogen, or 40 to 50% less fibrinogen than the polyester aloneaccording to the fibrinogen ELISA protocol. In yet other embodiments,the compositions according to the invention adsorb 5 to 45% lessfibrinogen, 10 to 45% less fibrinogen, 15 to 45% less fibrinogen, 20 to45% less fibrinogen, 25 to 45% less fibrinogen, 30 to 45% lessfibrinogen, 35 to 45% less fibrinogen, or 40 to 45% less fibrinogen thanthe polyester alone according to the fibrinogen ELISA protocol. In yetother embodiments, the compositions according to the invention adsorb 5to 40% less fibrinogen, 10 to 40% less fibrinogen, 15 to 40% lessfibrinogen, 20 to 40% less fibrinogen, 25 to 40% less fibrinogen, 30 to40% less fibrinogen, or 35 to 40% less fibrinogen than the polyesteralone according to the fibrinogen ELISA protocol. In yet otherembodiments, the compositions according to the invention adsorb 5 to 35%less fibrinogen, 10 to 35% less fibrinogen, 15 to 35% less fibrinogen,20 to 35% less fibrinogen, 25 to 35% less fibrinogen, or 30 to 35% lessfibrinogen than the polyester alone according to the fibrinogen ELISAprotocol. In yet other embodiments, the compositions according to theinvention adsorb 5 to 30% less fibrinogen, 10 to 30% less fibrinogen, 15to 30% less fibrinogen, 20 to 30% less fibrinogen, or 25 to 30% lessfibrinogen than the polyester alone according to the fibrinogen ELISAprotocol.

In certain embodiments, the compositions according to the invention havea coefficient of friction (COF) of less than 0.50, of less than 0.40, ofless than 0.35, of less than 0.30, of less than 0.25, of less than 0.24,of less than 0.23, of less than 0.22, of less than 0.21, of less than0.20, of less than 0.19, of less than 0.18, or of less than 0.17. Inother embodiments, the compositions according to the invention have aCOF of 0.15 to 0.50, 0.16 to 0.50, 0.17 to 0.50, 0.18 to 0.50, 0.19 to0.50, 0.20 to 0.50, 0.21 to 0.50, 0.22 to 0.50, 0.23 to 0.50, 0.24 to0.50, 0.25 to 0.50, or 0.30 to 0.50. In yet other embodiments, thecompositions according to the invention have a COF of 0.15 to 0.40, 0.16to 0.40, 0.17 to 0.40, 0.18 to 0.40, 0.19 to 0.40, 0.20 to 0.40, 0.21 to0.40, 0.22 to 0.40, 0.23 to 0.40, 0.24 to 0.40, 0.25 to 0.40, or 0.30 to0.40. In yet other embodiments, the compositions according to theinvention have a COF of 0.15 to 0.35, 0.16 to 0.35, 0.17 to 0.35, 0.18to 0.35, 0.19 to 0.35, 0.20 to 0.35, 0.21 to 0.35, 0.22 to 0.35, 0.23 to0.35, 0.24 to 0.35, 0.25 to 0.35, or 0.30 to 0.35.

The COF may be measured with a Bruker™ tribometer using a 1″×1″×0.125″plaque on a 4″×4″×0.125″ plaque under a 3 N normal load at 1.2mm/second.

In one embodiment, the polyesters useful in the invention exhibit aductile-to-brittle transition temperature of less than 0° C. based on a10-mil notch in a ⅛-inch thick bar as defined by ASTM D256.

In one embodiment, the articles of manufacture of the invention can beany device known in the art in which one or more of the physicalcharacteristics of any of the polyester compositions of the inventiondescribed herein are useful including but not limited to devices,containers, bottles, film and/or sheet, etc.

In one embodiment, any of these articles of manufacture can be used forthe medical industry, health care industry, pharmaceutical industry,food industry, bioprocessing industry, or any other industry in whichthe properties of the polymer compositions of the invention can beuseful.

Specific potential articles of manufacture and/or packaging can include,for example, medical packaging and/or articles and/or devices,pharmaceutical packaging and/or articles and/or devices, other healthcare packaging and/or articles and/or devices, packaging and/or articlesand/or devices for bioprocessing, food packaging and/or articles and/ordevices made therefrom, for example, medical devices for such asthermoformed trays, sterile or non-sterile packaging, steamsterilization bags or pouches, blood bags, tubing, catheters, bloodtherapy tubes, medical laboratory devices, medical or health diagnosticdevices, oxygenators, glucose sensor strips. By “medical”, veterinarianapplications are contemplated as well applications for the benefit ofhumans.

The medical devices can include but are not limited to components forinfusion and intravenous systems, extracorporeal oxygenators, renaldialyzers, catheters, and heart assist devices.

In one embodiment, the medical device can be an intravenous device orcomponent.

“Intravenous component,” as used herein, refers to components made froma polymeric material used for administering fluids (e.g., medicaments,nutrients) to the bloodstream of a patient (human and/or animal). In oneembodiment, the intravenous component is a rigid component.

In one embodiment, two-port, three-port and four-port stopcocks arecontemplated.

In one embodiment, the intravenous device or component can be astopcock. In one embodiment, a stopcock can be an externally operatedvalve regulating the flow of a liquid or gas through a pipe or tube. Inone embodiment, a stopcock can regulate the flow of intravenous fluidsinto a human being or into an animal.

Exemplary intravenous components include y-site connector assemblies,luer components, filters, stopcocks, manifolds, and valves. A y-siteconnector has a “Y” shape including a first arm having a first passage,a second arm having a second passage, and a third arm connected withsaid first and second arms and having a third passage communicating withsaid first and second passages. Luer components can include luer locks,connections, and valves.

In one embodiment, the medical device, for example, an intravenouscomponent, can withstand sterilization treatments, such as high pressuresteam sterilization, ethylene oxide gas sterilization, radiationsterilization, and dry-heating sterilization. In one embodiment, themedical device, for example, an intravenous component, has at least oneproperty chosen from toughness, good optical clarity, good chemicalresistance, good lubricity (the capacity to reduce friction and/orproperties of a lubricant) such as having a low coefficient of friction(COF), good anti-protein binding properties, reduced fibrinogenadsorption, good heat resistance, and good hydrolytic stability.

Other medical devices are also contemplated which may come into contactwith bodily fluids and/or blood components and/or any specimen oftissue, bone, organ, cartilage, etc. that can be removed from the humanbody. For certain of these medical devices, compatibility with bloodand/or other bodily fluids and/or other biological material is animportant characteristic.

Methods of making the articles of manufacture and/or devices of theinvention include but are not limited to: injection blow molding,injection molding, compression, extrusion, extrusion blow molding,casting, etc. or any other method known to one of ordinary skill in theart

Intravenous component(s) can include, for example, injection blow moldedintravenous component(s), compression molded intravenous components, andinjection molded intravenous component(s).

The polyester portion of the polyester compositions useful in theinvention can be made by processes known from the literature such as,for example, by processes in homogenous solution, by transesterificationprocesses in the melt, and by two phase interfacial processes. Suitablemethods include, but are not limited to, the steps of reacting one ormore dicarboxylic acids with one or more glycols at a temperature of100° C. to 315° C. at a pressure of 0.1 to 760 mm Hg for a timesufficient to form a polyester. See U.S. Pat. No. 3,772,405 for methodsof producing polyesters, the disclosure regarding such methods is herebyincorporated herein by reference.

The fluoroalkyl derivatives of this invention include but are notlimited to ones having the general formula:

-   -   wherein n=an integer from 8 to 30.

In one embodiment of the invention, the fluoroalkyl derivative can bePM-870 additive commercially available from 3M, St. Paul, Minn. ThisPM-870 additive is believed to contain mixtures of the above describedstructure. In particular, PM-870 is believed to contain 88-90 wt % ofthe fluoroalkyl derivatives, 10-12 wt % of polyethylene (CAS No.9002-88-4), <2 wt % of carboxylic acid(s), and <0.5 wt % of1,1,2,2,3,3,4,4,4-nonafluoro-N-(2-hydroxyethyl)-N-1-methyl-1-butanesulfonamide(CAS No. 34454-97-2). Thus, in one embodiment, the fluoroalkylderivatives useful in this invention may be mixed with polyethylene(e.g., 10-12 wt %) and optionally one or more carboxylic acids and1,1,2,2,3,3,4,4,4-nonafluoro-N-(2-hydroxyethyl)-N-1-methyl-1-butanesulfonamidebefore incorporation into the polyester.

In the polymer compositions of the invention, the fluoroalkylderivative(s) described herein may be present in an amount of 0.01 to 99weight % or 0.01 to 95 weight % or 0.01 to 90 weight % or 0.01 to 85weight % or 0.01 to 80 weight % or 0.01 to 75 weight % or 0.01 to 70weight % or 0.01 to 65 weight % or 0.01 to 60 weight % or 0.01 to 55weight % or 0.01 to 50 weight % or 0.01 to 45 weight % or 0.01 to 40weight % or 0.01 to 35 weight % or 0.01 to 30 weight % or 0.01 to 25weight % or 0.01 to 20 weight % or 0.01 to 15 weight % or 0.01 to 10weight % or 0.01 to 5 weight %, or 0.01 to 4 weight %, or 0.01 to 3weight %, or 0.01 to 2 weight %, or 0.01 to 1 weight %, or 0.01 to 3weight %, based on the total weight percentage of the polyester and thefluoroalkyl additive in the final polymer composition equaling 100weight %.

In the polymer compositions of the invention, the fluoroalkylderivative(s) described herein may be present in an amount of 0.01 to 99weight % or 0.01 to 95 weight % or 0.5 to 90 weight % or 0.5 to 85weight % or 0.5 to 80 weight % or 0.5 to 75 weight % or 0.5 to 70 weight% or 0.5 to 65 weight % or 0.5 to 60 weight % or 0.5 to 55 weight % or0.5 to 50 weight % or 0.5 to 45 weight % or 0.5 to 40 weight % or 0.5 to35 weight % or 0.5 to 30 weight % or 0.5 to 25 weight % or 0.5 to 20weight % or 0.5 to 15 weight % or 0.5 to 10 weight % or 0.5 to 9 weight% or 0.5 to 8 weight %, or 0.5 to 7 weight %, or 0.5 to 6 weight % or0.5 to 5 weight %, or 0.5 to 4 weight % or 0.5 to 3 weight % or 0.5 to 2weight % or 0.5 to 1 weight %, based on the total weight percentage ofthe polyester and the fluoroalkyl additive in the final polymercomposition equaling 100 weight %.

In the polymer compositions of the invention, the fluoroalkylderivative(s) described herein may be present in an amount of 1 to 99weight % or 1 to 95 weight % or 1 to 90 weight % or 1 to 85 weight % or1 to 80 weight % or 1 to 75 weight % or 1 to 70 weight % or 1 to 65weight % or 1 to 60 weight % or 1 to 55 weight % or 1 to 50 weight % or1 to 45 weight % or 1 to 40 weight % or 1 to 35 weight % or 1 to 30weight % or 1 to 25 weight % or 1 to 20 weight % or 1 to 15 weight % or1 to 10 weight % or 1 to 9 weight % or 1 to 8 weight %, or 1 to 7 weight%, or 1 to 6 weight %, or 1 to 5 weight %, or 1 to 4 weight %, or 1 to 3weight % or 1 to 2 weight %, or 1 to 1 weight %, based on the totalweight percentage of the polyester and the fluoroalkyl additive in thefinal polymer composition equaling 100 weight %.

In the polymer compositions of the invention, the fluoroalkylderivative(s) described herein may be present in an amount of 2 to 99weight % or 2 to 95 weight % or 2 to 90 weight % or 2 to 85 weight % or2 to 80 weight % or 2 to 75 weight % or 2 to 70 weight % or 2 to 65weight % or 2 to 60 weight % or 2 to 55 weight % or 2 to 50 weight % or2 to 45 weight % or 2 to 40 weight % or 2 to 35 weight % or 2 to 30weight % or 2 to 25 weight % or 2 to 20 weight % or 2 to 15 weight % or2 to 10 weight % or 2 to 9 weight % or 2 to 8 weight %, or 2 to 7 weight%, or 2 to 6 weight %, or 2 to 5 weight %, or 2 to 4 weight %, or 2 to 3weight %, based on the total weight percentage of the polyester and thefluoroalkyl additive in the final polymer composition equaling 100weight %.

In the polymer compositions of the invention, the fluoroalkylderivative(s) described herein may be present in an amount of 5 to 99weight % or 5 to 95 weight % or 5 to 90 weight % or 5 to 85 weight % or5 to 80 weight % or 5 to 75 weight % or 5 to 70 weight % or 5 to 65weight % or 5 to 60 weight % or 5 to 55 weight % or 5 to 50 weight % or5 to 45 weight % or 5 to 40 weight % or 5 to 35 weight % or 5 to 30weight % or 5 to 25 weight % or 5 to 20 weight % or 5 to 15 weight % or5 to 10 weight %, In the polymer blend of the invention, the fluoroalkylderivative(s) described herein may be present in an amount of 10 to 99weight % or 10 to 95 weight % or 10 to 90 weight % or 10 to 85 weight %or 10 to 80 weight % or 10 to 75 weight % or 10 to 70 weight % or 10 to65 weight % or 10 to 60 weight % or 10 to 55 weight % or 10 to 50 weight% or 10 to 45 weight % or 10 to 40 weight % or 10 to 35 weight % or 10to 30 weight % or 10 to 25 weight % or 10 to 20 weight % or 10 to 15weight %, based on the total weight percentage of the polyester and thefluoroalkyl additive in the final polymer composition equaling 100weight %.

In the polymer compositions of the invention, the fluoroalkylderivative(s) described herein may be present in an amount of 15 to 99weight % or 15 to 95 weight % or 15 to 90 weight % or 15 to 85 weight %or 15 to 80 weight % or 15 to 75 weight % or 15 to 70 weight % or 15 to65 weight % or 15 to 60 weight % or 15 to 55 weight % or 15 to 50 weight% or 15 to 45 weight % or 15 to 40 weight % or 15 to 35 weight % or 15to 30 weight % or 15 to 25 weight %, based on the total weightpercentage of the polyester and the fluoroalkyl additive in the finalpolymer composition equaling 100 weight %.

The invention further relates to the polyester compositions of theinvention being blended with another polymer. The blend comprises:

(a) 5 to 99.99 weight % of at least one of the polyesters describedherein; and

(b) 0.01 to 95 weight % of at least one fluoroalkyl derivative;

(c) optionally, another polymer component which is not the at least onepolyester described in (a).

The invention further relates to the a blend comprising:

(a) 5 to 99.98 weight % of at least one of the polyesters describedherein; and

(b) 0.01 to 95 weight % of at least one fluoroalkyl derivative; and

(c) 0.01 to 95 weight % optionally, another polymer component which isnot the at least one polyester described in (a),

based on the total weight percentage of the polyester(s) useful in theinvention, any other polymers, and the fluoroalkyl additive in the finalpolymer composition equaling 100 weight %.

Suitable examples of other polymeric components than can be present inthe polyester compositions of the invention include, but are not limitedto, nylon, polyesters different from those described herein,polyethylene, polypropylene, polyamides such as ZYTEL® from DuPont;polystyrene, polystyrene copolymers, styrene acrylonitrile copolymers,acrylonitrile butadiene styrene copolymers, poly(methylmethacrylate),acrylic copolymers, poly(ether-imides) such as ULTEM® (apoly(ether-imide) from General Electric); polyphenylene oxides such aspoly(2,6-dimethylphenylene oxide) or poly(phenylene oxide)/polystyreneblends such as NORYL 1000® (a blend of poly(2,6-dimethylphenylene oxide)and polystyrene resins from General Electric); polyphenylene sulfides;polyphenylene sulfide/sulfones; poly(ester-carbonates); polycarbonatessuch as LEXAN® (a polycarbonate from General Electric); polysulfones;polysulfone ethers; and poly(ether-ketones) of aromatic dihydroxycompounds; or mixtures of any of the other foregoing polymers. Theblends can be prepared by conventional processing techniques known inthe art, such as melt blending or solution blending. However, thepolyester blends useful in the invention can either containpolycarbonate or not. In one embodiment, polycarbonate is not present inthe polyester blends of the invention.

The polycarbonates useful in the polyester compositions of the inventionalso may be copolyestercarbonates such as those described in U.S. Pat.Nos. 3,169,121; 3,207,814; 4,194,038; 4,156,069; 4,430,484, 4,465,820,and 4,981,898, the disclosure regarding copolyestercarbonates from eachof the U.S. Patents is incorporated by reference herein.

Copolyestercarbonates useful in this invention can be availablecommercially and/or can be prepared by known methods in the art. Forexample, they can be typically obtained by the reaction of at least onedihydroxyaromatic compound with a mixture of phosgene and at least onedicarboxylic acid chloride, especially isophthaloyl chloride,terephthaloyl chloride, or both.

In addition, the polymer compositions in this invention may also containfrom 0.01 to 25% by weight of the overall composition common additivessuch as colorants, dyes, mold release agents, flame retardants,plasticizers, nucleating agents, stabilizers, including but not limitedto, UV stabilizers, thermal stabilizers and/or reaction productsthereof, fillers, and impact modifiers.

In addition, the polymer compositions in this invention can also containadditives common in the applicable industry, for example, antimicrobialadditives for the medical industry and/or health care industry and/orpharmaceutical industry.

The polymer compositions of the invention can include mold releaseagents that are commonly used in the art, including but not limited to,calcium stearate, stearic acid, and zinc stearate. While any amount ofmold release agent can be used, in some embodiments, amounts of 0.10 to5 weight % or 0.25 to 1 weight %, of the mold release agent can be usedwhere the mold release agent and the polymer composition equal a totalof 100 weight %.

Examples of typical commercially available impact modifiers well knownin the art and useful in this invention include, but are not limited to,ethylene/propylene terpolymers; functionalized polyolefins, such asthose containing methyl acrylate and/or glycidyl methacrylate;styrene-based block copolymeric impact modifiers, and various acryliccore/shell type impact modifiers. Residues of such additives are alsocontemplated as part of the polyester composition.

The polyester compositions of the invention can comprise at least onechain extender. Suitable chain extenders include, but are not limitedto, multifunctional (including, but not limited to, bifunctional)isocyanates, multifunctional epoxides, including for example, epoxylatednovolacs, and phenoxy resins. In certain embodiments, chain extendersmay be added at the end of the polymerization process or after thepolymerization process. If added after the polymerization process, chainextenders can be incorporated by compounding or by addition duringconversion processes such as injection molding or extrusion. The amountof chain extender used can vary depending on the specific monomercomposition used and the physical properties desired but is generallyabout 0.1 percent by weight to about 10 percent by weight, preferablyabout 0.1 to about 5 percent by weight, based on the total weigh of thepolyester.

Thermal stabilizers are compounds that stabilize polyesters duringpolyester manufacture and/or post polymerization, including, but notlimited to, phosphorous compounds, including, but not limited to,phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid,phosphonous acid, and various esters and salts thereof. The esters canbe alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkylethers, aryl, and substituted aryl. In one embodiment, the number ofester groups present in the particular phosphorous compound can varyfrom zero up to the maximum allowable based on the number of hydroxylgroups present on the thermal stabilizer used. The term “thermalstabilizer” is intended to include the reaction product(s) thereof. Theterm “reaction product” as used in connection with the thermalstabilizers of the invention refers to any product of a polycondensationor esterification reaction between the thermal stabilizer and any of themonomers used in making the polyester as well as the product of apolycondensation or esterification reaction between the catalyst and anyother type of additive. These can be present in the polyestercompositions useful in the invention.

Reinforcing materials may be useful in the compositions of thisinvention. The reinforcing materials may include, but are not limitedto, carbon filaments, silicates, mica, clay, talc, titanium dioxide,Wollastonite, glass flakes, glass beads and fibers, and polymeric fibersand combinations thereof. In one embodiment, the reinforcing materialsare glass, such as, fibrous glass filaments, mixtures of glass and talc,glass and mica, and glass and polymeric fibers.

The following examples further illustrate how polyester compositions ofthe invention can be made and evaluated, and are intended to be purelyexemplary of the invention and are not intended to limit the scopethereof.

EXAMPLES

Unless indicated otherwise, parts are parts by weight, temperature is indegrees Celsius (° C.) or is at room temperature, and pressure is at ornear atmospheric pressure.

The inherent viscosity (IV) of the polyesters was determined in a 60/40(wt/wt) phenol/tetrachloroethane solution at a concentration of 0.5g/100 mL at 25° C.

As used herein, the abbreviation “wt” means “weight.”

Unless stated otherwise, the glass transition temperature (T_(g)) wasdetermined using a TA DSC 2920 instrument from Thermal AnalystInstruments at a scan rate of 20° C./min according to ASTM D3418.

The glycol content and the cis/trans ratio of the polyesters weredetermined by proton nuclear magnetic resonance (NMR) spectroscopy.

Unless otherwise specified, the cis/trans ratio of1,4-cyclohexanedimethanol in the following polyesters was approximately30/70, and could range from 35/65 to 25/75. Unless otherwise specified,the cis/trans ratio of 2,2,4,4-tetramethyl-1,3-cyclobutanediol in thefollowing polyesters was approximately 50/50.

ASTM D638 procedure was used to determine the tensile properties.Tensile properties include tensile strength at yield, tensile strengthat break (ultimate tensile strength), tensile modulus (Young's modulus),and elongation at yield and break. Tensile strength at yield is themaximum stress at which permanent, non-elastic deformation begins. Yieldpoint is the point (load) at which the material yields, i.e., increasein strain occurs without an increase in stress. Ultimate tensilestrength is the maximum stress a material can withstand before failing.Elongation at yield is the strain that the material undergoes at theyield point, or the percent change in length that occurs while thematerial is stressed to its yield point. Elongation at break is thestrain at failure, or the percent change in length at failure. Tensile(or Young's) modulus, is the ratio of stress to strain within theelastic region of the stress-strain curve (prior to the yield point).

ASTM D790 procedure was used to determine the flexural properties.

ASTM D256 procedure was used to determine the Izod impact strength(notched) at 23° C.

ASTM D1003 procedure was used to determine the total transmittance andhaze. The measurements were made on injection molded plaques havingdimensions of 4″×4″×0.125″.

L*, a*, and b* color coordinates were measured on transparent injectionmolded plaques having dimensions of 4″×4″×0.125″ using a HunterLabUltraScan XE® spectrophotometer. The spectrophotometer was operatedusing a D65 illuminant light source with a 10° observation angle andintegrating sphere geometry. The spectrophotometer was zeroed,standardized, UV calibrated, and verified in control. The colormeasurement was made in the total transition (TTRAN) mode. The L* valueindicates the transmission/opacity of the sample. The a* value indicatesthe redness (+)/greenness (−) of the sample. The b* value indicates theyellowness (+)/blueness (−) of the sample.

Table 1 below lists the materials that were used in the followingexamples, their abbreviations, and main ingredient.

TABLE 1 Material Abbreviation Main Ingredient Fluoroalkyl A1 Mixture offluoroalkyl derivatives of the general Additive formula:

where n = 8 to 30. (Commercially available, e.g., from 3M under productname Repellent Polymer Melt Additive PM-870.) Base Polymer P1Copolyester comprising: 100 mole % TPA residues;  22 mole % TMCDresidues;  78 mole % CHDM residues; and IV = 0.63 dL/g. Base Polymer P2Copolyester comprising:  35 mole % IPA residues;  65 mole % TPAresidues; 100 mole % CHDM residues; and IV = 0.72 dL/g. Base Polymer P3Copolyester comprising: 100 mole % TPA residues;  69 mole % EG residules 31 mole % CHDM residues; and IV = 0.75 dL/g. Base Polymer P4Copolyester comprising: 100 mole % of TPA residues;  38 mole % EGresidues;  62 mole % CHDM residues; and IV = 0.73 dL/g.

As used herein, “TPA” refers to terephthalic acid, “TMCD” refers to2,2,4,4-tetramethyl-1,3-cyclobutanediol, “CHDM” refers to1,4-cyclohexanedimethanol, “IPA” refers to isophthalic acid, and “EG”refers to ethylene glycol.

Example 1

A1 was compounded with P1 in a twin-screw extruder to form a concentratecontaining 8 wt % of A1 and pelletized after extrusion.

The 8 wt % concentrate was blended with additional P1 to form mixturescontaining 0.5 wt %, 1 wt %, 2 wt %, 3 wt %, 4 wt %, and 5 wt % of A1before injection molding.

The blends of P1 containing 0.5 to 5 wt % of A1 along with a controlmade of 100 wt % of P1 were injection molded into flexural bars with aToyo 90 injection molding machine following the manufacturer'srecommended processing conditions.

The flexural bars were subjected to a fibrinogen ELISA (enzyme-linkedimmunosorbent assay) to evaluate their fibrinogen binding behavior. Thetesting protocol is described below.

General Test Description

ELISA is an immunological assay used to detect the presence of abiomolecule, such as a protein, in a sample. In practice, proteins arephysically adsorbed onto the flexural bar surface when the bars areinserted into a disposable microtiter plate. Then, in a separatemicrotiter plate, an antibody is applied over the same surface andallowed to bind to the protein. The degree of antibody binding isdetermined by the amount of the enzyme that is conjugated to theantibody. Detection of that enzyme amount is typically through the useof a chromogenic substrate for the enzyme. The extent of color change isproportional to the amount of adsorbed protein present and is typicallymeasured spectrophotometrically using a plate reader.

Test Fixture

The fibrinogen ELISA experimental setup was designed and developedspecifically for ELISA of flexural bars. The testing was used toevaluate the degree of protein adsorption of each substrate. A fixturewas developed to allow consistent and convenient testing of polymerflexural bars with the dimensions of 5″×½″×⅛″ (length×width×thickness ininches). The polymer bars were mounted in the fixture prior to testing.Unlike a typical ELISA where a series of reagents are successively addedand removed from a microwell plate, this method allowed the simultaneousmovement of 24 bars held in the fixture through a series of microwellplates that contained the various ELISA reagents.

The fixture 10 is shown in the FIGURE. The fixture 10 was made of twoaluminum plates 12 and 14, which were connected at the corners with fourmetal rods 16. Each plate 12, 14 contained 24 holes corresponding to thewell positions of a standard 24-well microtiter plate (not shown). Theupper plate 12 held the polymer bars 19 in recesses 13 on the undersideof the plate 12. When mounted, the bars protruded through the lowerplate holes 18 and into the microplate wells (not shown). The lowerplate 14 was constructed with a recessed well (not shown) that acts as abase resting on the testing microplate (not shown). A base plate 20holds the testing microplate (now shown) and connects with the lowerplate 14 via four short metal rods 21.

Fibrinogen ELISA Sample Preparation

Prior to ELISA, all sample bars were wiped with a lint-free tissue,moistened with sterile, deionized water, and re-dried with tissue. Thecleaned test bars were then seated completely into the recesses of thetest fixture and allowed to remain in place throughout the assay as thefixture was moved from one reagent to another in separate plates.

ELISA Procedure

The ELISA protocol was designed for the specific detection of fibrinogenadsorption to solid polymer substrates. The ELISA was initiated byincubating the polymer sample bars in an aqueous solution of fibrinogen(0.5 mg/mL in a 2% bovine serum albumin (w/v) phosphate-buffered salinesolution prepared in a blocked tube) for five minutes at 37° C. Theunbound fibrinogen was removed by three successive washes inphosphate-buffered saline (PBS). The sample bars were then incubated ina non-animal protein blocking agent (NAP) for 30 minutes at 37° C. toblock unoccupied binding sites on the substrate. The sample bars werethen incubated for one hour at 37° C. in the presence of ananti-fibrinogen, horseradish peroxidase antibody-conjugate (1 μg/mL) ina NAP blocked microtiter plate. After that, successive washes of thebars in a diluted TBST buffer were used to remove excess non-specificbinding of the antibody-conjugate. In the final step of the ELISAprocedure, the sample bars were incubated with the enzyme substrate(3,3′,5,5′-tetramethylbenzidine). After 1 hour, the test fixture and thesample bars were removed from the microplate containing the enzymesubstrate. Using a microplate spectrophotometer, absorbance measurementsof the enzyme substrate wells were made at 630 nm to detect conversionof the enzyme substrate to the blue product. Fibrinogen binding valuesof various polymers were then inferred from the amount of enzymesubstrate conversion and calculated relative to the polymer withoutadditive after subtracting the background absorbance readings.

Each individual test included four replicate bars for each polymersample. P1 without A1 was used as the universal control sample for allstudies.

With regard to data interpretation, higher initial fibrinogen proteinadsorption would indicate that the sample is more likely to inducehigher level of platelet adhesion and platelet activation, whichsubsequently lead to thrombus and blood coagulation. Meanwhile, apolymer substrate with lower initial fibrinogen adsorption is expectedto exhibit better hemocompatibility.

The fibrinogen ELISA data was analyzed using Dunnett's test to determinethe statistical significance, when compared to the P1 control. (C. W.Dunnett, “A Multiple Comparison Procedure for Comparing SeveralTreatments with a Control,” J. Am. Statistical Assoc., Vol. 50, p. 1096(1955).)

In statistics, when performing a hypothesis test, a p-value helps todetermine the significance of the results. Hypothesis tests are used totest the validity of a claim that is made about a population. The claimthat is on trial is called the null hypothesis, and usually is a claimthat there is no effect or difference in what is being tested. Allhypothesis tests ultimately use a p-value to weigh the strength of theevidence (i.e., what the data are saying about the population). Thep-value is a number between 0 and 1. A small p-value (typically ≦0.05)indicates strong evidence against the null hypothesis, so the nullhypothesis can be rejected. A large p-value (>0.05) indicates weakevidence against the null hypothesis, so the null hypothesis cannot berejected. A p-value very close to the cutoff (0.05) is considered to bemarginal.

In data analysis, most authors refer to a p-value of <0.05 as beingstatistically significant, meaning the risk of incorrectly concludingthere is a difference is less than 1 in 20 (or a 95% confidence in theconclusion). Thus, in this example, a p-value of <0.05 indicates astatistically significant difference between the treated sample and thecontrol.

The results of the ELISA study are reported in Table 2.

TABLE 2 Percentage of Fibrinogen Adsorption Reduction Weight Percentageof A1 in P1 0.5 1 2 3 4 5 Test 1 26% 36% 11% 21% 30% 35% (p: 0.0116) (p:0.0018) (p: 0.3549) (p: 0.0608) (p: 0.0009) (p: 0.0003) Test 2 30% 39%24% 31% 45% 35% (p: 0.0061) (p: 0.0013) (p: 0.03) (p: 0.008) (p:<0.0001) (p: 0.0002) Test 3 12% 15% 32% 24% 30% 38% (p: 0.3029) (p:0.1735) (p: 0.002) (p: 0.0739) (p: 0.0278) (p: 0.0004) Average 23% 30%22% 25% 35% 36% Standard  9% 13% 11%  5%  9%  2% Deviation

As seen from Table 2, all of the A1 compounded samples showed positivefibrinogen adsorption reduction compared to the control P1 alone, andmost results were statistically significant.

Example 2

The procedure of Example 1 was repeated except that P1 was replaced withP2, P3, and P4. A 5 wt % A1 concentrate was made with each polymer,which was then diluted with their respective base polymers to formsamples with A1 at loading levels ranging from 0.5 to 5 wt %. The blendswere then injection molded into flexural bars and subjected tofibrinogen ELISA. The control for each sample tested was the basepolymer for that sample without A1.

The results of the ELISA study are reported in Table 3.

TABLE 3 Percentage of Fibrinogen Adsorption Reduction FibrinogenAdsorption Sample Reduction P-Value P2 + 0.5 wt % A1 15% ± 12% 0.0885P2 + 1 wt % A1 26% ± 8%  0.0043 P2 + 1.5 wt % A1 38% ± 11% 0.0002 P2 + 2wt % A1 32% ± 10% 0.0071 P2 + 5 wt % A1 31% ± 12% 0.0078 P3 + 1 wt % A115% ± 19% 0.4076 P3 + 2 wt % A1 23% ± 19% 0.1726 P4 + 0.5 wt % A1  6% ±16% 0.744 P4 + 1 wt % A1 17% ± 4%  0.0943 P4 + 1.5 wt % A1 17% ± 6% 0.1006

As seen from Table 3, all A1 compounded samples showed positivefibrinogen adsorption reduction compared to the control sample of P2,P3, or P4 alone. Samples of P2 with 1-5 wt % of A1 yielded statisticallysignificant fibrinogen reduction relative to their control.

Example 3

The blends of P1 with various loadings of A1 prepared in Example 1 wereformed into 1″×1″×0.125″ (length×width×depth in inches) and 4″×4″×0.125″plaques. For each A1 loading level, the plaques were loaded into aBruker™ tribometer and tested for their coefficient of friction (COF).The plaques were placed under a load of 3 N, and the 1″×1″×0.125″ plaquewas moved at a rate of 1.2 mm/sec across the surface of the 4″×4″×0.125″plaque. Each A1 loading level was run in triplicate with new plaques ineach test.

The COF results are reported in Table 4.

TABLE 4 Amount of A1 in P1 Coefficient of Friction Standard Deviation 00.694 0.273 (control) 0.5 wt %   0.308 0.055 1 wt % 0.242 0.036 2 wt %0.234 0.046 3 wt % 0.216 0.087 4 wt % 0.180 0.058 5 wt % 0.166 0.057

As seen from Table 4, adding A1 lowered the COF of P1.

Example 4

An injection-molded sample of P1 containing 2 wt % of A1 was Gammasterilized (50 kGy) and then submitted for three tests under the ISO10993 series of standards for biocompatibility evaluation: (1)cytotoxicity test; (2) intracutaneous injection test; and (3) Kligmanmaximization test. The injection-molded sample passed all three tests.

Example 5

The IV and Tg of P1 alone and of P1 with A1 at several compoundinglevels were measured. The results are reported in Table 5.

TABLE 5 IV T_(g) Amount of A1 in P1 (dL/g) (° C.) 0 wt % 0.607^(a)103.4^(a) 0.5 wt %   — 102.9^(a) 1 wt % 0.596^(a) 100.7^(a) 2 wt %0.591^(a) 96.3^(a) 3 wt % — 94.3^(a) 4 wt % — 89.5^(a) 5 wt % 0.574^(a)83.3^(a) 8 wt % 0.553^(a)/0.565^(b) 77.7^(a) ^(a)flexural bar(dimensions - 5 in. × 0.5 in. × 0.125 in.) ^(b)pellet

As seen from Table 5, at low loading levels of A1, the IVs of theinjected molded samples were very similar. Moreover, the IV of thepellet at 8 wt % of A1 was very similar to that of the injection moldedflexural bar at the same loading level. Furthermore, the Tg of thesamples decreased as the concentration of A1 increased.

Example 6

The tensile properties of P1, P2, P3, and P4 alone and of these polymerswith A1 at several compounding levels were determined. The results arereported in Table 6.

TABLE 6 Tensile Properties Elongation Elongation Break @ Yield @Strength Break Strength Yield Modulus Sample (MPa) (%) (MPa) (%) (MPa)P1 52 210 43.2 7 1575 (control) P1 + 0.5 wt % A1 50.1 ± 1.4 155.4 ± 13.744.6 ± 0.05 5.3 ± 0.03 1564 ± 3.9 P1 + 1 wt % A1   48 ± 1.3 143.9 ± 8.9645.6 ± 0.05   5 ± 0.02 1620 ± 5.8 P1 + 2 wt % A1 50.4 ± 0.5 161.3 ± 16.246.6 ± 0.09 4.9 ± 0.01 1625 ± 12.3 P1 + 3 wt % A1 48.8 ± 1.5 147.8 ±14.3 48.1 ± 0.03 4.6 ± 0.01 1670 ± 7.5 P1 + 4 wt % A1   45 ± 5.4 126.5 ±27.1 49.5 ± 0.02 4.5 ± 0.02 1702 ± 6.2 P1 + 5 wt % A1 45.4 ± 6.0 129.7 ±30.5 50.4 ± 0.06 4.4 ± 0.02 1725 ± 11.4 P1 + 8 wt % A1 34.4 ± 3.1  84.2± 40.8 52.8 ± 0.22 4.4 ± 0.02 1770 ± 8.7 P2 51.0 300.0 47.0 5.0 1815(control) P2 + 0.5 wt % A1 32.1 ± 1.4 239.4 ± 8.2 49.5 ± 0.07   4 ± 0.011807 ± 3 P2 + 1 wt % A1 31.9 ± 1.6 242.4 ± 10.9 50.1 ± 0.06   4 ± 0.021804 ± 4 P2 + 1.5 wt % A1 31.4 ± 1.8 234.2 ± 13.3 50.7 ± 0.1 4.1 ± 0.011792 ± 5 P2 + 2 wt % A1 30.6 ± 0.9 239.6 ± 12.8 51.3 ± 0.11 4.1 ± 0.011779 ± 7 P2 + 5 wt % A1 30.6 ± 1.5 171.3 ± 10   54 ± 0.07 4.4 ± 0.011714 ± 3 P3 28.0 110.0 50.0 4.3 1873 (control) P3 + 1 wt % A1 25.1 ± 0.7219.8 ± 13 50.3 ± 0.05 3.9 ± 0.02 1922 ± 5 P3 + 2 wt % A1 30.9 ± 4.9299.3 ± 67.3 51.3 ± 0.08   4 ± 0.02 1932 ± 16 P4 52.0 330.0 45.0 5.01800 (control) P4 + 0.5 wt % A1   34 ± 2.6 235.1 ± 20.1 49.4 ± 0.14   4± 0.00 1859 ± 29 P4 + 1 wt % A1 32.4 ± 1.7 231.7 ± 8.2 49.9 ± 0.08   4 ±0.01 1791 ± 13 P4 + 1.5 wt % A1 31.6 ± 0.3 234.9 ± 3.0 50.1 ± 0.08   4 ±0.01 1796 ± 6

Example 7

The Izod impact strength of P1, P2, P3, and P4 alone and of thesepolymers with A1 at several compounding levels were determined. Theresults are reported in Table 7.

TABLE 7 Izod Impact Strength No Break Sample (J/m) Percentage P1 860 100(control) P1 + 0.5 wt % A1 889.9 100 P1 + 1 wt % A1 930.3 100 P1 + 2 wt% A1 964.2 100 P1 + 3 wt % A1 1006.9 100 P1 + 4 wt % A1 1029.4 100 P1 +5 wt % A1 95.3 0 P1 + 8 wt % A1 72.0 0 P2 80.0 0 (control) P2 + 0.5 wt %A1 84.4 0 P2 + 1 wt % A1 66.3 0 P2 + 1.5 wt % A1 65.4 0 P2 + 2 wt % A159.4 0 P2 + 5 wt % A1 31.0 0 P3 101.0 50 (control) P3 + 1 wt % A1 77.2 0P3 + 2 wt % A1 55.3 0 P4 no break 100 (control) P4 + 0.5 wt % A1 76.2 0P4 + 1 wt % A1 78.1 0 P4 + 1.5 wt % A1 67.9 0

As seen from Table 7, there was minimal change in the Izod impactstrength of polymer P1 compounded with A1 at concentrations up to 4 wt%. The Izod impact strength of polymers P2, P3 and P4 compounded with A1decreased as the concentration of A1 increased.

Example 8

The flexural strength of P1 alone and of P1 with A1 at severalcompounding levels were determined. The results are reported in Table 8.

TABLE 8 Flexural Properties Amount of Elongation @ Break Break StrengthModulus A1 in P1 (%) (MPa) (MPa) 0.5 wt %   7.004 72.706 1703.5 1 wt %7.006 74.201 1751.5 2 wt % 7.005 75.129 1823.9 5 wt % 7.003 77.4371919.2 8 wt % 7.004 74.727 1951.9

Example 9

The haze, transmittance, and color values of P1 alone and of P1 with A1at several compounding levels were determined. The results are reportedin Table 9.

TABLE 9 Amount of Haze Transmittance A1 in P1 L* a* b* (%) (%) 0 wt %95.54 −0.16 0.63 0.51 90.9 0.5 wt %   95.71 −0.26 0.82 0.45 91.7 1 wt %95.69 −0.34 1.1 0.51 91.7 2 wt % 95.51 −0.44 1.86 0.56 91.2 3 wt % 94.96−0.75 3.67 9.12 90 4 wt % 94.7 −0.92 4.81 6.29 89.3 5 wt % 94.76 −0.73.9 3.89 90 8 wt % 81.66 0.38 16.09 41 64.4

As seen from Table 9, the samples maintained low haze, b* values, andtransmittance up to about 2 wt % loading of A1.

The invention has been described in detail with reference to theembodiments disclosed herein, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

What is claimed is:
 1. A polymer composition comprising: (I) at leastone polyester which comprises: (a) a dicarboxylic acid componentcomprising: i) 70 to 100 mole % of terephthalic acid residues; ii) 0 to30 mole % of aromatic dicarboxylic acid residues having up to 20 carbonatoms; and iii) 0 to 10 mole % of aliphatic dicarboxylic acid residueshaving up to 16 carbon atoms; and (b) a glycol component comprising2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, wherein the total mole% of the dicarboxylic acid component is 100 mole %, the total mole % ofthe glycol component is 100 mole %; and wherein the inherent viscosityof the polyester is from 0.1 to 1.2 dL/g as determined in 60/40 (wt/wt)phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.;and (II) at least one fluoroalkyl derivative; wherein said polymercomposition comprises a blend of (I) and (II).
 2. The polymercomposition according to claim 1 comprising 1,4-cyclohexanedimethanolresidues.
 3. The polymer composition according to claim 2 comprising1,4-cyclohexanedimethanol residues and ethylene glycol residues.
 4. Thepolymer composition according to claim 2 comprising ethylene glycolresidues.
 5. The polymer composition of claim 2 wherein the glycolcomponent comprises 50 to 85 mole % 1,4-cyclohexanedimethanol residuesand 15 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. 6.The polymer composition of claim 2 wherein the glycol componentcomprises 60 to 85 mole % 1,4-cyclohexanedimethanol residues and 15 to40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
 7. Thepolymer composition of claim 1 wherein the acid component comprisingisophthalic acid residues.
 8. The polymer composition of claim 1 whereinsaid fluoroalkyl derivative is mixed with polyethylene.
 9. The polymercomposition of claim 1 wherein said fluoroalkyl derivative is present inthe amount of 0.01 to 8 weight % based on the total weight percentage ofsaid polyester and said fluroalkyl derivative.
 10. The polymercomposition of claim 1 wherein said fluoroalkyl derivative is present inthe amount of 0.01 to 5 weight % based on the total weight percentage ofsaid polyester and said fluroalkyl derivative.
 11. The polymercomposition of claim 1 or 2 which adsorbs at least 5% less fibrinogencompared to the polyester alone according to a fibrinogen enzyme-linkedimmunosorbent assay (ELISA) protocol, which protocol comprises thefollowing steps: (1) incubating the polymer sample in flexural bar formin a phosphate-buffered saline solution containing 0.5 mg/mL offibrinogen and 2% of bovine serum albumin (w/v) for 5 minutes; (2)removing unbound fibrinogen from the sample bar by washing the bar withphosphate-buffered saline having a pH of 7.3 three times; (3) incubatingthe sample bar in a non-animal protein blocking agent for 30 minutes at37° C.; (4) incubating the bar in a 1 μg/mL solution of ananti-fibrinogen horseradish peroxidase antibody-conjugate in anon-animal protein-blocked microtiter plate for 60 minutes at 37° C.;(5) washing the bar four times with a diluted TBST buffer to removeexcess non-specific binding of the antibody-conjugate; (6) incubatingthe bar with an enzyme substrate 3,3′,5,5′-tetramethylbenzidine for 60minutes; (7) removing the bar from the microplate containing the enzymesubstrate; and (8) measuring the absorbance of the enzyme substrate inthe microplate well using a microplate spectrophotometer at 630nanometers to detect conversion of the enzyme substrate to the blueproduct.
 12. The polymer compositions of claim 2 which adsorbs from 15%to 45% less fibrinogen compared to the polyester alone.
 13. The polymercompositions of claim 1 or 12 which have a coefficient of friction ofless than 0.50 as measured with a Bruker™ tribometer using a1″×1″×0.125″ plaque on a 4″×4″×0.125″ plaque under a 3 N normal load at1.2 mm/second.
 14. The polymer compositions of claim 1 or 12 which havea coefficient of friction (COF) of 0.10 to 0.50 as measured with aBruker™ tribometer using a 1″×1″×0.125″ plaque on a 4″×4″×0.125″ plaqueunder a 3 N normal load at 1.2 mm/second.
 15. An article of manufacturemade with the polymer composition of claim 1 or
 2. 16. The article ofclaim 15 which is selected from a medical article, pharmaceuticalarticle, veterinarian article, bioprocessing article, or a food article.17. The article of claim 15 which is a medical device.
 18. The articleof claim 15 which is an intravenous component.
 19. The polymercomposition of claim 6, wherein said fluoroalkyl derivative is presentin the amount of 0.01 to 5 weight % based on the total weight percentageof said polyester and said fluroalkyl derivative.
 20. The polymercomposition of claim 19, wherein said polymer exhibits a notched Izodimpact strength of at least (400 J/m) 7.5 ft-lb/in at 23° C. with a10-mil notch in a 3.2 mm (⅛-inch) thick bar determined according to ASTMD256.